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. 2026 Aug 3;21(15):e70922. doi: 10.1002/asia.70922

Recent Advances in Direct Elimination of Carboxylic Acids to Olefins

Yi Zhou 1, Zhanzhou Wei 1, Yabing Zhang 1, Yunfei Zhang 1, Kehan He 2
PMCID: PMC13431371  PMID: 42545843

ABSTRACT

The direct elimination of carboxylic acids to olefins offers an atom‐economical and sustainable strategy for synthesizing valuable alkenes from abundant, stable, and inexpensive precursors. This review systematically summarizes recent advances (through 2025) in reaction systems and mechanistic studies in this transformation, encompassing thermal, transition metal catalysis (e.g., Rh, Pd, Ir, Ni, Cu, Fe), photochemical, and electrochemical pathways. Within this framework, we highlight progress in catalyst design—including ligand optimization and the development of earth‐abundant metal and rare metal catalysts—activation modes (e.g., through the formation of anhydrides, or via direct decarboxylation), and the implementation of greener reaction conditions. While significant progress has been made in thermal and transition metal‐catalyzed methods, challenges persist, including cost, metal recovery, and the need for harsh conditions. Emerging photochemical and electrochemical approaches provide milder and more environmentally benign alternatives; however, issues regarding selectivity, scalability, and reagent sustainability demand further investigation. This overview aims to serve as a comprehensive knowledge base and practical reaction guide, inspiring future research to overcome existing limitations and advance the practical, sustainable synthesis of olefins via elimination of carboxylic acids.

Keywords: carboxylic acids, decarbonylation, decarboxylation, elimination, olefins


This review presents a comprehensive roadmap for synthesizing olefins via elimination of carboxylic acids. It organizes diverse strategies—thermal, transition‐metal‐catalyzed, photocatalytic, and electrochemical—within a unified framework. The discussion highlights advances in catalyst design, mechanistic understanding, and greener protocols, offering a critical knowledge base for sustainable alkene production.

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1. Introduction

Olefins serve as indispensable building blocks in organic synthesis, underpinning the construction of polymers, pharmaceuticals, and advanced functional materials [1, 2]. Consequently, the ongoing development of efficient and selective strategies for their preparation remains a central objective in synthetic chemistry. While classical methods such as the elimination of alkyl halides or the dehydration of alcohols are well‐established, they often rely on stoichiometric reagents, generate stoichiometric waste, and can lack regioselectivity [3]. In this context, the direct transformation of readily available, stable, and often renewable carboxylic acids into olefins via a decarboxylative elimination represents a highly attractive and sustainable alternative. This approach provides inherent atom economy, with CO2 as the primary byproduct, and has consequently attracted significant research interest in recent years [4, 5]. Driven by these advantages, considerable progress has been made in developing diverse catalytic platforms for this transformation, as illustrated conceptually in Scheme 1. Initial breakthroughs in thermal and transition‐metal‐catalyzed (e.g., Rh, Pd, Ir, Ni, Cu, Fe) systems established foundational mechanisms and demonstrated feasibility, often through in situ activation of the acid via mixed anhydrides. Subsequent innovations have focused on overcoming limitations related to harsh conditions and catalyst cost. The emergence of photoredox catalysis has enabled the use of light to drive decarboxylation under remarkably mild conditions, frequently in synergy with transition metals to orchestrate complex reaction sequences. Parallel advancements in electrocatalysis leverage electrons as traceless redox agents, opening avenues for green and potentially scalable protocols. Across these paradigms, continuous refinement of catalysts, ligands, and conditions has progressively enhanced control over reactivity, regioselectivity, and functional group tolerance. This review aims to provide a systematic and critical overview of these developments, organizing the discussion within a unified framework encompassing thermal, transition‐metal‐catalyzed, photocatalytic, and electrochemical strategies, and to offer perspectives on future challenges in the field.

SCHEME 1.

SCHEME 1

Different strategies for the elimination of carboxylic acids to form alkenes.

This review aims to provide a systematic and comprehensive overview of recent progress (up to 2025) in synthesizing olefins from carboxylic acids via direct decarboxylative elimination or formal decarboxylative elimination. We organize the discussion within a unified framework encompassing four principal activation modes: thermal induction, transition metal catalysis, photocatalysis, and electrocatalysis. For each category, we summarize key reaction systems, discuss mechanistic insights, and highlight advances in catalyst design (including earth‐abundant metals) and greener reaction conditions. Distinguishing itself from previous reviews that often focus on a specific catalytic mode [6, 7, 8, 9], this work integrates these diverse strategies into a single, hierarchical discussion. This structure not only facilitates comparison across different methodologies but also allows for the timely inclusion of the latest developments. By presenting a consolidated knowledge map and practical reaction guide, this review seeks to inform and inspire future research aimed at overcoming existing challenges—such as selectivity, scalability, and sustainability—in the practical application of carboxylic acids for olefin synthesis.

2. Method of Producing Alkenes by Elimination of Carboxylic Acids

This section categorizes and examines the principal strategies developed for the elimination of carboxylic acids to alkenes. The discussion is organized according to the key energy input or catalytic system employed, progressing from conventional thermal activation to more contemporary catalytic approaches. We begin with the thermal decarboxylation methods, followed by sections dedicated to transition metal catalysis, photocatalysis, and electrocatalysis.

2.1. Thermal Decarboxylation

In 1968, Kochi first reported the decarboxylative elimination of carboxylic acids to olefins [10]. However, the method's reliance on toxic lead tetraacetate and high temperatures restricted its broader application (Scheme 2a). The development of alternative methods under milder conditions is therefore of significant interest. Inspired by prior studies on the generation of acyl radicals via hypervalent iodine reagents in photoredox catalysis [11], in 2016, Liu and co‐workers reported a novel, transition metal‐free approach for the direct decarboxylative elimination of aryl carboxylic acids under microwave irradiation [12]. They demonstrated that commercially available PhI(OCOCF3)2 serves as an effective oxidant, enabling the synthesis of various aryl‐ and diaryl‐substituted olefins in moderate to good yields. A plausible reaction mechanism is illustrated in Scheme 2b. Initially, reaction of carboxylic acid 1a with PhI(OCOCF3)2 forms the hypervalent iodine dicarboxylate intermediate 1A. Homolytic cleavage of this intermediate generates a carboxyl radical 1B and iodobenzene. Subsequent decarboxylation of 1B yields the key alkyl radical 1C, which is then oxidized (via single‐electron transfer) to the corresponding carbocation 1D. Given the stoichiometric requirement of 1.2 equivalents of PIFA and the redox‐inactive nature of the PhI byproduct, it can be inferred that PIFA itself serves as the terminal oxidant. Specifically, the oxidation is mediated by the residual hypervalent iodine species present in the medium. Finally, regioselective deprotonation of 1D furnishes the desired alkene product 2a, with the reported conditions favoring the formation of the (E)‐isomer.

SCHEME 2.

SCHEME 2

Preparation of alkenes by thermal decarboxylation.

2.2. Preparation of Olefins by Transition Metal Catalysis

Transition metal catalysis has proven to be a highly effective and versatile strategy for elimination of carboxylic acids, enabling precise control over reactivity and selectivity under often milder conditions than purely thermal methods. The activation of the carboxylic acid substrate is a key mechanistic step. Based on this, the following discussion is organized into two main categories: anhydride‐assisted catalysis and direct (anhydride‐free) catalysis (Scheme 3).

SCHEME 3.

SCHEME 3

Two strategies for transition metal‐catalyzed elimination of carboxylic acids to form olefins.

Anhydride‐assisted strategies typically involve the in situ formation of a mixed or symmetric anhydride from the carboxylic acid prior to engagement with the metal catalyst. This pre‐activation step lowers the C─COOH bond cleavage energy barrier and facilitates the subsequent oxidative addition, often allowing for milder reaction conditions and broader substrate tolerance. In contrast, direct catalysis involves the coordination and activation of the carboxylic acid or carboxylate salt by the metal center, which can offer superior atom‐ and step‐economy but may present greater challenges in C─COOH bond cleavage. More precise catalyst design and condition regulation are often needed to achieve efficient conversion. The following sections detail developments within each paradigm.

2.2.1. Anhydride‐Assisted Transition Metal Catalysis

This subsection traces the evolution of anhydride‐assisted elimination, progressing from pioneering noble metal systems to more recent, cost‐effective alternatives.

2.2.1.1. Rhodium‐Catalyzed Preparation of Olefins

In this field, there is a reaction that does not employ anhydride as a carboxylic acid activator, yet the reaction mechanism is proposed to proceed via an anhydride intermediate. In 1976, Foglia and Barr investigated this transformation using rhodium, a group VIII metal known for its high activity in carbonylation (and thus potentially its reverse, decarbonylation) reactions [13]. They found that a catalyst system composed of RhCl3 and triphenylphosphine (PPh3) efficiently converted stearic acid to heptadecene at 280°C–285°C under a nitrogen atmosphere. Spectroscopic and elemental analysis identified the active catalytic species as chlorocarbonylbis(triphenylphosphine)rhodium(I) [(PPh3)2Rh(CO)Cl]. A proposed mechanism is outlined in Scheme 4a. The reaction is initiated by the thermal formation of a stearic anhydride intermediate 3A. This anhydride undergoes oxidative addition to Rh(I) to form an acyl‐rhodium(III) species 3B. Decarbonylation of 3B releases CO and yields a five‐coordinate alkyl‐rhodium(III) complex 3C, which can then rearrange to the six‐coordinate alkyl‐rhodium(III) complex 3D. Finally, β‐hydride elimination and reductive elimination from 3D release the olefin product and regenerate the original Rh(I) catalyst. It was noted that an excess of PPh3 was crucial for maintaining catalyst stability throughout this cycle. This seminal study established a key mechanistic blueprint for anhydride‐assisted decarbonylative elimination, highlighting the role of in situ anhydride formation and subsequent oxidative addition in facilitating the critical C─C bond cleavage step. In later work in 1993, Miller and co‐workers further confirmed this process (Scheme 4b) [14]. They introduced additional acetic anhydride as an acid activator and improved the overall yield and selectivity, avoiding competing olefin isomerization through in situ distillation techniques.

SCHEME 4.

SCHEME 4

Rh‐catalyzed decarbonylation via anhydride intermediate.

2.2.1.2. Palladium‐Catalyzed Preparation of Olefins

A significant advancement was reported by Miller and co‐workers in 1993 [14]. They developed a method for the selective decarbonylation/dehydration of fatty carboxylic acids to the corresponding terminal alkenes via a mixed anhydride intermediate. The carboxylic acid was first treated with an equimolar amount of acetic anhydride to form the mixed anhydride, which was subsequently converted to the alkene product at 250°C using the Pd catalysts (Scheme 5). The continuous removal of alkene products by distillation effectively suppressed side reactions such as isomerization. Furthermore, this protocol was applicable to various natural fatty acids and functionally substituted substrates, enabling the synthesis of odd‐carbon‐chain α‐alkenes from renewable resources and providing a complementary, sustainable pathway to petroleum‐based chemicals.

SCHEME 5.

SCHEME 5

Pd‐catalyzed decarbonylation via anhydride intermediate by Miller's group.

Despite the advances, the high reaction temperature (ca. 250°C) necessitated the use of excess ligand and specialized continuous distillation apparatus to suppress alkene isomerization. Addressing this limitation, Gooßen and colleagues introduced a pivotal mild‐condition protocol in 2004 [15]. Their strategy employed pivalic anhydride to activate carboxylic acids in situ via the formation of mixed anhydrides. These intermediates successfully underwent decarbonylation and β‐hydride elimination at a significantly lower temperature of 110°C, catalyzed by PdCl2 and the bidentate phosphine ligand DPE‐Phos, yielding the corresponding alkene along with CO, CO2, and pivalic acid (Scheme 6a). The authors proposed a catalytic cycle involving oxidative addition of the mixed anhydride to a Pd(0) species to generate an acyl‐palladium intermediate, decarbonylation to form an alkyl‐palladium complex, and final β‐hydride elimination to release the alkene product and regenerate the Pd(0) catalyst. Notably, product isomerization was extremely slow under these milder conditions, effectively avoiding the formation of internal alkenes and enhancing selectivity. This reaction eliminated the need for traditional high‐temperature distillation techniques, offered easier operation and a broad substrate scope, and provided an efficient and practical new route to alkenes from readily available carboxylic acids. Further optimization followed. In 2010, Scott and co‐workers found the addition of trialkylamine was beneficial for the stability of catalytic species, leading to improved reaction efficiency (Scheme 6b) [16].

SCHEME 6.

SCHEME 6

Palladium/DPE‐Phos catalyzed decarbonylative elimination reaction.

Further research efforts shifted toward reducing catalyst and ligand loading. In 2012, Tolman's team reported a highly efficient protocol for converting biomass‐derived carboxylic acids to alkenes using only 0.25 mol% of PdCl2 and 2.2 mol% of ligand within a short reaction time of 2 h (Scheme 7a) [17]. The catalyst loading could be further reduced to 0.005 mol% without a substantial decrease in yield, although the reaction time increased accordingly. Remarkably, the yield of styrene did not decrease significantly even when using unpurified reagents or under an air atmosphere. These results clearly demonstrated the excellent tolerance of this decarbonylation reaction to air and moisture, enabling efficient production without strict anhydrous or anaerobic conditions. This greatly enhanced the practicality and sustainability of the method, offering a low‐energy, easy‐to‐operate synthetic pathway for biomass conversion.

The deep mechanistic understanding of this reaction was achieved by Cramer's team through computational studies. In 2016, they conducted a comprehensive density functional theory (DFT) investigation (Scheme 7b) [18]. The process initiates with the endergonic reaction by +1.0 kcal mol 1 between hydrocinnamic acid 15 and pivalic anhydride to form the mixed anhydride intermediate 17 and pivalic acid. Intermediate 17 then enters the catalytic cycle, which comprises four key elementary steps: (i) oxidative addition, (ii) decarbonylation, (iii) alkene formation, and (iv) catalyst regeneration. The study further revealed that the steric bulk of the phosphine ligand significantly influenced reaction kinetics, and larger ligands lowered the activation barrier. In contrast, the structure of the auxiliary anhydride had a negligible effect on efficiency. A critical finding was the strong coordination of CO to the palladium center, forming a stable Pd–CO intermediate that dramatically increased the energy barrier for subsequent steps and led to catalyst deactivation, underscoring the importance of CO removal in practical applications.

SCHEME 7.

SCHEME 7

(a) Pd‐catalyzed decarbonylation of carboxylic acids with low catalyst and ligand loading; (b) mechanistic study.

Concurrently, efforts to develop well‐defined catalyst systems culminated in the work of Jensen and co‐workers in 2016 [19]. They developed a class of structurally well‐defined palladium precatalysts bearing diphosphine ligands, such as Pd(cinnamyl)Cl(DPE‐Phos), for the decarbonylative elimination of fatty acids to linear α‐olefins (Scheme 8a). This system achieved high catalytic efficiency without the need for excess phosphine ligands.

SCHEME 8.

SCHEME 8

Pd precatalysts for decarbonylative dehydration of fatty acids to linear α‐olefins with different solvents. (a) with DMPU; (b) with γ‐valerolactone (GVL).

Despite these multiple improvements, the persistent use of expensive and hazardous solvents (e.g., DMPU) remained a concern [20]. Driven by the principles of green chemistry, the search for alternative solvents gained importance. In 2019, Jensen's team made progress in this direction by screening various bio‐based solvents for the decarbonylative dehydration of fatty acids to linear α‐olefins [21]. They identified γ‐valerolactone (GVL) as a compatible alternative due to its high polarity, aprotic nature, and high boiling point (Scheme 8b). GVL, characterized by low toxicity, high stability, food‐grade safety, and sustainable production from lignocellulosic biomass, achieved comparable efficiency to traditional toxic solvents. Mechanistic studies suggested that GVL promoted carbonylative dissociation and β‐hydride transfer by stabilizing charge‐separated transition states, thereby maintaining high activity and selectivity. Although challenges remained regarding avoiding the stoichiometric activation of the substrate and catalyst recycling, this work provided a promising strategy for the green conversion of fatty acids.

Besides activation by anhydrides, other activating reagents have also been developed and applied for carboxylic acid activation. A highly innovative activation mode was introduced by Zhang's team in 2024. They developed a versatile carboxylic acid decarboxylative functionalization platform based on the combination of sulfuryl fluoride (SO2F2) and palladium catalysis, enabling decarboxylative dehydrogenation of alkyl carboxylic acids (Scheme 9) [22]. The core of this strategy lies in the rapid generation of a highly reactive acyl fluoride intermediate from SO2F2 and the carboxylic acid under mild conditions, which then initiates the palladium catalytic cycle. Through DFT calculations and experimental verification, the key steps were clarified as oxidative addition of the acyl fluoride, decarbonylation, followed by β‐hydride elimination. The proposed mechanism begins with the reaction of the alkyl carboxylic acid and SO2F2 to generate the reactive acyl fluoride intermediate 15B. This is followed by oxidative addition of the C─F bond of the acyl fluoride to a Pd0 species, affording intermediate 15C. Subsequent decarbonylation of 15C yields the alkylpalladium complex 15D, which then undergoes β‐hydride elimination to give the π‐complex 15E. Finally, reductive elimination from 15E releases the olefin product 16 together with HF and regenerates the active Pd0 catalyst. This method avoids separate formation of a preactivated intermediate, exhibits a broad substrate scope, has been successfully applied to the late‐stage functionalization of drug molecules, and has been extended to SuFEx click chemistry systems. It provides a general and atom‐economical synthetic pathway for the efficient transformation of carboxylic acids.

SCHEME 9.

SCHEME 9

Pd‐catalyzed decarboxylative dehydrogenation of carboxylic acids using sulfuryl fluoride.

2.2.1.3. Iridium‐Catalyzed Preparation of Olefins

Beyond palladium and rhodium, iridium has also demonstrated unique utility, particularly in controlling alkene isomerization outcomes.

In 2011, Ryu and co‐workers explored the iridium‐catalyzed decarbonylation of aliphatic carboxylic acids [23]. They found that the complex IrCl(CO)(PPh3)2 efficiently catalyzed the reaction at 250°C in the presence of KI. However, this was accompanied by rapid double‐bond isomerization, leading to the formation of internal alkenes with randomly distributed double‐bond positions. The introduction of acetic anhydride as an activator and a reduction in temperature to 160°C effectively inhibited isomerization, allowing the reaction to terminate at the initial decarbonylation product and yielding terminal alkenes selectively. The decarbonylation and isomerization mechanism of long‐chain aliphatic carboxylic acids is outlined in Scheme 10. The process begins with the oxidative addition of the C(O)─O bond of the acid anhydride—formed in situ from two carboxylic acid molecules or from carboxylic acid and Ac2O via condensation—to generate the acyl iridium complex 9B. Subsequently, complex 9B undergoes decarbonylation, yielding the alkyl iridium complex 9C. A β‐hydride elimination from 9C then produces a terminal alkene 11 along with the iridium hydride complex 9D. Reductive elimination of carboxylic acid from 9D regenerates the iridium(I) catalyst. Concurrently, the iridium hydride species 9D catalyzes the isomerization of the terminal alkene to internal alkenes through the formation of the alkyl iridium intermediate 9F. This strategy provided a flexible route to selectively access either terminal or internal alkenes from the same precursor by simply adjusting additives and temperature.

SCHEME 10.

SCHEME 10

IrCl(CO)(PPh3)2‐catalyzed decarbonylation of fatty acids to generate alkenes.

Given the combination of acetic anhydride and potassium iodide could promote the decarbonylation of aliphatic carboxylic acids catalyzed by iridium, Hapiot's team in 2015 focused on optimizing reaction conditions for the decarbonylation of bio‐sourced unsaturated fatty acids [24]. Their detailed study, conducted under mild conditions (160°C, 5 h) in the presence of KI and Ac2O (Scheme 11), revealed that substrate purity significantly impacted catalytic efficiency. High‐purity oleic acid (99%) achieved 95% conversion and a terminal alkene selectivity of 91:9, while performance declined with lower‐purity feedstock (70%). The structure of the phosphine ligand was crucial, with PPh3 proving optimal; substituents on the phenyl rings (especially ortho‐substituents) or the use of bidentate ligands severely inhibited the reaction. An optimized combination of Ac2O (2 equiv.) and KI (0.5 equiv.) was key to achieving high conversion and selectivity. The catalytic system could be recovered and recycled via distillation, with activity partially restorable by ligand replenishment. The broad applicability of this strategy to various unsaturated fatty acids and dicarboxylic acids was demonstrated, offering an efficient and sustainable pathway to linear α‐olefins from renewable resources.

SCHEME 11.

SCHEME 11

Ir/PPh3‐catalyzed decarbonylation of biosourced unsaturated fatty acids.

2.2.1.4. Nickel‐Catalyzed Preparation of Olefins

Driven by cost considerations, the development of catalysts based on earth‐abundant metals has gained momentum [25]. In 2016, Tolman's team reported a nickel‐based system for converting biomass‐derived carboxylic acids to olefins (Scheme 12) [26]. Through a combination of high‐throughput and conventional experimentation, they screened an efficient catalytic system employing Nickel precursors with aryl phosphine ligands. This system successfully achieved the conversion of nonanoic acid to octene at 180°C–190°C with 78% yield and 90% selectivity. Mechanistic studies suggest that regeneration of the active [Ni‐ligand] catalytic species via CO dissociation is the rate‐limiting step in the sequence. This work provided a new strategy using a low‐cost metal and laid a foundation for subsequent catalyst design.

SCHEME 12.

SCHEME 12

Nickel‐catalyzed decarboxylation of carboxylic acids to alkenes.

2.2.1.5. Iron‐Catalyzed Preparation of Olefins

Among inexpensive metals, iron is particularly attractive due to its natural abundance and low toxicity [27]. In 2012, the Ryu group reported an iron‐catalyzed decarbonylation of aliphatic carboxylic acids to α‐olefins [28]. Using FeCl2 as the catalyst, DPPPent as the ligand, in the presence of KI and Ac2O at 240°C, the reaction achieved up to 97% selectivity for α‐olefins (Scheme 13). The substrate scope encompassed C14–C22 straight‐chain fatty acids and some functionalized carboxylic acids, demonstrating good functional group tolerance. Mechanistic studies indicated that the reaction did not proceed via a radical pathway. The catalytic cycle commences with the condensation of carboxylic acid 9 and Ac2O to form the intermediate acid anhydride 9G. Subsequently, an iron–carbonyl complex (generated in situ from FeCl2, a phosphine ligand, KI, and CO) reacts with 9G to yield the acyl iron complex 9H. Decarbonylation of 9H then affords the alkyl iron complex 9I, which undergoes β‐hydride elimination to produce α‐olefins 11 along with the iron hydride species 9J. Reductive elimination from 9J regenerates the active catalytic complex. Concurrently, the iron hydride species 9J can catalyze the isomerization of the initially formed α‐olefins 11 to give internal olefins. This work successfully replaced precious metals with an inexpensive iron catalyst to achieve a highly selective transformation, offering a green and economical strategy for synthesizing α‐olefins from renewable resources with significant synthetic and industrial potential.

SCHEME 13.

SCHEME 13

Iron catalyzes decarbonylation of aliphatic carboxylic acids to α‐olefins.

2.2.2. Anhydride ‐Free Transition Metal Catalysis

As mechanistic understanding of decarbonylative reactions has deepened, research has expanded towards more direct and atom‐economical pathways that bypass the need for stoichiometric activators such as anhydride [29, 30, 31]. These “anhydride‐free” strategies often involve the direct activation of carboxylic acids or their derivatives (e.g., esters) by the transition metal catalyst, offering potential advantages in step count and waste reduction. This section highlights representative methods developed under this paradigm, showcasing diverse metal catalysts and innovative mechanistic pathways.

In 2017, Tolman's group reported a palladium‐catalyzed, highly selective decarbonylation of fatty acid para‐nitrophenyl esters, which serve as activated substrates without exogenous anhydride (Scheme 14) [32]. Systematic screening revealed that a dual‐ligand system composed of XantPhos and IPr played a synergistic role: the bidentate binding mode and flexible coordination of XantPhos promoted the rapid dissociation of α‐olefins following β‐hydride elimination, effectively inhibiting the olefin isomerization pathway and thereby significantly enhancing α‐selectivity. In contrast, IPr accelerated the reaction rate and substrate conversion by facilitating the oxidative addition step. This reaction was applicable to various fatty acid ester substrates under relatively mild conditions, basically achieving α‐selectivity greater than 98%. Combined with density functional theory (DFT) calculations, the study further elucidated the microscopic mechanism of ligand‐mediated reaction pathway control, clarifying the crucial role of the bulkiness of IPr combined with the flexible mono‐ or bidentate nature of XantPhos in preventing olefin re‐coordination and isomerization. A plausible mechanism for the Pd‐catalyzed decarbonylation of ester 24a to afford either allylbenzene 13 (cycle I) or β‐methylstyrene (cycle II) is illustrated in Scheme 14 (L = IPr, XantPhos). The cycle begins with oxidative addition of 24a to PdL2, forming the Pd‐acyl species 24A. Decarbonylation of 24A gives the Pd‐alkyl intermediate 24B, which then undergoes β‐hydride elimination to yield the key Pd‐hydride species 24C bearing a coordinated alkene. In cycle I, dissociation of the alkene from 24C releases the terminal alkene product 13, and after loss of CO and deprotonation (by the liberated p‐nitrophenolate), the Pd° catalyst is regenerated. Alternatively, cycle II proceeds via rotation of the alkene ligand in 24C about the Pd···C═C axis, leading to intermediate 24D. Subsequent migratory insertion generates the alkylpalladium species 24E, which undergoes benzylic β‐hydride elimination to form the internal‐alkene‐coordinated intermediate 24F. Finally, release of the alkene from 24F affords β‐methylstyrene with concomitant loss of CO and deprotonation, restoring the active Pd catalyst. This work provides a catalytic route with high selectivity and practicality for the efficient preparation of linear α‐olefins from renewable fatty acids.

SCHEME 14.

SCHEME 14

The selective decarbonylation of fatty acid esters produces linear α‐olefins.

Concurrently, the same group developed a nickel‐catalyzed transformation of carboxylic acids to alkenes that operates without added sacrificial acceptors [33]. It successfully achieved the efficient conversion of various fatty acids to the corresponding linear α‐alkenes. Using Ni(acac)2 or Ni(OAc)2 as catalysts yields olefins with a maximum yield of 82% and an α‐selectivity of 70%. Further studies introduced 1,1,3,3‐tetramethyldisiloxane (TMDS) and Cu(OTf)2 to enable a catalytic cycle for PPh3, enhancing the practicality of the process (Scheme 15). Mechanistic investigations indicated that the reaction proceeds via a decarbonylation pathway, wherein PPh3 acts as a terminal reductant and is oxidized to OPPh3. This strategy offers a mild and highly selective sustainable route for converting biomass‐derived carboxylic acids into valuable alkenes.

SCHEME 15.

SCHEME 15

Nickel‐catalyzed transformation of carboxylic acids to alkenes without anhydride additives.

Recent work has uncovered novel mechanisms that diverge from classical paradigms. In 2023, the Hoover team reported a copper‐catalyzed decarboxylative elimination of hydrocinnamic acids to styrenes, achieved through the synergistic effect of CuOAc/bpy and MnO2 without the need for precious metal photocatalysts or stoichiometric heavy metal additives (Scheme 16) [34]. Mechanistic studies revealed that the reaction pathway differed from the conventional single‐electron transfer mechanism. Instead, it proceeded via benzyl deprotonation to form a benzyl anion, followed by copper‐mediated single‐electron transfer to generate a benzyl radical, which subsequently underwent a radical decarboxylation step to yield the target olefin. This work provides a new reaction mechanism and catalytic strategy for decarboxylative elimination reactions.

SCHEME 16.

SCHEME 16

Copper‐catalyzed decarboxylative elimination of carboxylic acids to styrenes.

2.3. Photocatalytic Preparation of Olefins

While decarboxylative/decarbonylative elimination has traditionally relied on transition‐metal catalysis and elevated temperatures, these methods can be limited by environmental impact, cost, moderate yields, and non‐selective isomerization leading to product mixtures. In contrast, photocatalysis has emerged as a rapidly advancing field offering a sustainable alternative. By leveraging light as a traceless reagent, photocatalytic strategies often operate under mild conditions, providing precise control over reactive intermediates and enabling novel pathways that are inaccessible thermally. This section reviews recent progress in photocatalytic decarboxylative elimination, encompassing both exclusively photocatalytic systems and synergistic photoredox/transition‐metal dual catalysis.

2.3.1. Exclusively Photocatalytic Systems

This section focuses on photocatalytic strategies where the transformation is driven solely by the photoredox cycle, without the involvement of a catalytic transition metal cycle. In 2019, Tunge and co‐workers further reported a novel method for the decarboxylative elimination of amino acids to form enamides [35]. As illustrated in the proposed mechanism, the photoredox catalyst is initially activated upon light irradiation. The excited photocatalyst then oxidizes carboxylate 30A via single‐electron transfer (SET), generating a carboxyl radical 30B, which subsequently undergoes decarboxylation to afford carbon‐centered radical 30C. Two plausible pathways were proposed from this intermediate (Scheme 17). In Path A, radical 30C adds to the catalyst Cu (OAc)2, forming intermediate 30D. This species then undergoes either β‐hydride elimination or a Cu‐mediated E2‐type elimination to yield the enamine product 31. Alternatively, Path B involves the oxidation of radical 30C to a carbocation 30E, which finally undergoes deprotonation to give enamine 31. In summary, the Tunge Group successfully developed an environmentally benign and economically attractive photocatalytic oxidative decarboxylation route, offering a promising strategy for the synthesis of enamides and enecarbamates.

SCHEME 17.

SCHEME 17

Photoinduced decarboxylative elimination for the synthesis of enamides and enecarbamates from N‐acyl amino acids.

Building on foundational work in photoredox catalysis by the Glorius [36] and Leonori [37] groups, Tunge and colleagues further developed an innovative strategy in 2025 for the direct decarboxylative synthesis of enamides and enecarbamates [38]. Their method utilizes a radical decarboxylation initiated by an excited‐state organic photocatalyst, followed by a critical α‐amino radical‐mediated halogen atom transfer (XAT) step. The reaction, conducted under an argon atmosphere with visible light irradiation for four hours in the presence of cesium carbonate, delivers products in good to excellent yields. As outlined in Scheme 18, the proposed mechanism for the decarboxylative elimination begins with single‐electron oxidation of the α‐amido carboxylate (32A) by the photoredox catalyst. The resulting radical species undergoes rapid decarboxylation to generate the key α‐amido radical 32B. This radical then participates in a halogen‐atom transfer (XAT) event with the activated alkyl halide 33, yielding the bromoaminal intermediate 32C and concurrently producing an α‐nitro radical 32D. The reduced state of the photocatalyst subsequently reduces 32D to form the nitronate species 32E, thereby completing the photoredox catalytic cycle. In a parallel step, the bromoaminal intermediate 32C undergoes fast elimination of bromide to give a cationic iminium intermediate 32F, which is then deprotonated by the nitronate 32E. This sequence delivers the final enamide product 34 along with the nitroalkane 32G. Alternatively, the added Cs2CO3 base could also facilitate the deprotonation of 32F. In summary, the Tunge Group established a mild and efficient synthetic route to enamides and enecarbamates, eliminating the requirement for expensive transition‐metal catalysts and harsh reaction conditions.

SCHEME 18.

SCHEME 18

Photoredox‐catalyzed decarboxylative elimination of amino acids via HAT.

Beyond explicit photoredox catalysts, photoactive electron donor‐acceptor (EDA) complexes have emerged as powerful, fully organic platforms for radical generation [39, 40]. These complexes operate without discrete photocatalysts, typically through charge transfer within a transient complex between an electron donor and an electron acceptor under light irradiation. In 2021, Chen and colleagues introduced a novel EDA complex‐based strategy for converting carboxylic acid NHPI esters to alkenes, departing from conventional catalytic cycles (Scheme 19) [41]. They proposed that a weak interaction between the NHPI ester and NaI facilitates the formation of a photoactive electron donor–acceptor (EDA) complex 36B. Upon visible‐light excitation, this EDA complex undergoes single‐electron transfer (SET) to generate an alkyl radical 36C and an iodine radical. The iodine radical then abstracts a hydrogen atom from the alkyl radical to directly furnish the corresponding olefin 37. Alternatively, mechanistic studies also support a pathway wherein the alkyl radical is first trapped by the iodine radical to form an iodoalkane intermediate, which subsequently undergoes homolytic cleavage to yield the olefin product. This methodology represents a simple, robust, and green alternative, enabling the metal‐free and highly selective synthesis of alkenes from readily available carboxylic acids. It underscores the potential of EDA complex photochemistry as a versatile and sustainable pathway for olefin synthesis.

SCHEME 19.

SCHEME 19

Decarboxylative elimination enabled by electron donor–acceptor (EDA) complexes.

2.3.2. Synergistic Photoredox/Transition‐Metal Catalysis

The merger of photoredox catalysis with transition‐metal catalysis has unlocked powerful strategies for decarboxylative elimination. This synergistic approach combines the mild, redox‐umpolung capability of photocatalysis with the versatile bond‐forming and insertion chemistry of transition metals, enabling novel mechanistic pathways under exceptionally mild conditions [42]. This subsection highlights key developments across different metal systems, showcasing how this dual catalysis paradigm overcomes limitations inherent to single catalytic modes.

In 2018, inspired by Sorensen's work on alkane dehydrogenation via successive hydrogen atom transfer (HAT) [43], Tunge and colleagues developed a mild and cost‐effective system for converting amino acids and N‐acyl amino acids directly into enamides and enol carbamates (Scheme 20) [44]. This transformation synergistically combines an organic photoredox catalyst with a cobaloxime catalyst, facilitating radical decarboxylation coupled with hydrogen evolution, thereby avoiding stoichiometric oxidants. The proposed mechanism initiates with deprotonation of the amino acid by a Co(I) species to yield carboxylate 38B and Co(III)‐H. Subsequent photoinduced oxidation of 38B generates carboxyl radical 38C, which undergoes decarboxylation via single‐electron transfer mediated by the photoredox catalyst, affording the key α‐amino alkyl radical 38D. This radical then abstracts a hydrogen atom, producing the enamide product 39 and regenerating a Co(III)‐H2 species. Finally, hydrogen gas is released via a hydrogen evolution reaction (HER), regenerating the Co(I) catalyst. This work provides a direct, mild, and oxidant‐free route for synthesizing enamides and enecarbamates from readily available amino acid precursors.

SCHEME 20.

SCHEME 20

Decarboxylative elimination of N‐acyl amino acids via photoredox/cobalt dual catalysis.

Building on the development of dual‐catalytic systems for functionalized amino acids, Beil and colleagues reported an innovative nickel/photoredox strategy in 2026 that achieves distinct stereocontrol through the strategic use of aryl halides (Scheme 21) [45]. In this system, photoinduced oxidative decarboxylation of the amino acid generates an α‐aminoalkyl radical 40A, which is intercepted by an aryl–Ni(II) species 40G to form a sterically encumbered Ni(III) intermediate 40B. The introduction of aryl halides with tailored electronic and steric properties proves crucial, as they effectively divert the reaction pathway away from conventional reductive elimination toward intramolecular β‐hydride elimination, thereby yielding enamide products. A notable feature of this protocol is the multifaceted role of the iridium photocatalyst, which facilitates both the initial photoredox event and a subsequent Dexter energy transfer; the latter drives the in situ triplet‐state photoisomerization of the initially formed (E)‐enamides into (Z)‐configured isomers with high selectivity. This work not only elucidates the mechanistic bifurcation points within nickel photocatalysis but also introduces a versatile design dimension for orchestrating complex radical transformations, although the focus remains on functionalized substrates.

SCHEME 21.

SCHEME 21

Ni/photoredox co‐catalyzed decarboxylative elimination with divergent selectivity controlled by aryl halide.

While effective for functionalized substrates, the decarboxylative elimination of common aliphatic carboxylic acids to olefins with high selectivity remained challenging, often requiring harsh conditions and precious metals. To improve the reactivity of carboxylic acids, redox‐active esters were usually used. In this context, Glorius and co‐workers reported in 2018 a highly efficient and versatile dual organophotoredox/copper catalysis strategy for converting redox‐active esters into valuable olefins with high selectivity (Scheme 22) [46]. Their proposed mechanism begins with photoexcitation of the organophotocatalyst (OPC‐4), which, via single‐electron transfer (SET), reduces an activated aliphatic acid derivative 42. Decarboxylation then releases CO2 and generates an alkyl radical 42A. This radical is rapidly intercepted by a Cu(II) catalyst to form an alkylcopper(III) intermediate 42B. Reductive elimination from 42B releases the olefin product and yields a Cu(I) species 42C. Finally, a SET between the oxidized photocatalyst [OPC‐4]+ and 42C closes both catalytic cycles, regenerating the ground‐state OPC‐4 and the Cu(II) catalyst. This breakthrough enables efficient and highly selective decarboxylative olefination under mild, room‐temperature conditions.

SCHEME 22.

SCHEME 22

Decarboxylative elimination of active esters via organophotoredox/copper dual catalysis.

Beyond copper, palladium systems have also been integrated with photocatalysis to access novel reactivity. In 2018, the Fu group developed a method for the decarboxylative elimination of redox‐active esters into alkenes using a dual‐ligand palladium system under mild photochemical conditions (Scheme 23) [47]. They demonstrated that a catalyst system comprising PdCl2 with both a bidentate (Xantphos) and a monodentate (CyJohnPhos) ligand, in the presence of a base, efficiently furnishes various alkenes, including enol ethers and enamides, in good to excellent yields. A proposed mechanism involves a Pd(0) complex, coordinated by both ligands, transferring an electron to the redox‐active ester to trigger decarboxylation, generating a hybrid alkyl Pd(I) intermediate. Photoinduced dissociation of the weaker monodentate ligand creates a coordinatively unsaturated species that allows the alkyl group to adopt a geometry conducive to β‐hydride elimination. Following olefin release, the phosphine ligand recoordinates to regenerate the Pd(0) catalyst. This work underscores how strategic ligand design in concert with light irradiation can unlock previously inaccessible pathways in palladium catalysis.

SCHEME 23.

SCHEME 23

Irradiation‐induced palladium‐catalyzed decarboxylative elimination enabled by a dual ligand system.

Building upon extensive research in photoredox and proton‐reduction catalysis, Ritter and colleagues reported in 2018 the direct decarboxylative elimination of carboxylic acids to α‐olefins [48]. Through systematic screening, a dual catalytic system comprising the cobalt complex Co(dmgH)2(4‐OMe‐py)Cl (CO_1) and the photoredox catalyst Ir[dF(CF3)ppy]2(dtbpy)PF6 was identified as optimal. Under mild conditions, this cooperative system delivered α‐olefins in high yields. The proposed mechanism (Scheme 24) begins with deprotonation of carboxylic acid 5 to form carboxylate 5A. The photoexcited iridium photocatalyst then oxidizes 5A via single‐electron transfer (SET) to generate carboxyl radical 5B. Rapid decarboxylation yields the key alkyl radical 5C. This radical is intercepted by the cobalt catalyst, which facilitates its formal dehydrogenation, ultimately leading to the formation of the α‐olefin product 7 with concomitant evolution of H2. In summary, Ritter and co‐workers developed a promising, additive‐free strategy for the direct conversion of abundant carboxylic acids into valuable α‐olefins, providing a viable blueprint for related transformations.

SCHEME 24.

SCHEME 24

Direct decarboxylative elimination of general carboxylic acids via photoredox/ cobalt dual catalysis.

While homogeneous photoredox/transition‐metal dual catalysis has been extensively explored, heterogeneous hybrid systems offer potential advantages in catalyst stability and recyclability, yet remain underexplored [49]. Notably, the inexpensive, robust semiconductor TiO2 is known to promote decarboxylation via photoinduced hole oxidation [50]. Motivated by this, in 2025, Nozaki and colleagues developed a heterogeneous dual catalytic system combining TiO2 with a molecular cobalt complex for the highly selective conversion of carboxylic acids to α‐olefins [51]. As illustrated in Scheme 25, the proposed mechanism involves two synergistic pathways on TiO2. Photoexcitation generates electron‐hole pairs. The holes oxidize the carboxylic acid substrate 45 to an acyloxy radical, which decarboxylates to form an alkyl radical intermediate 45A. Concurrently, the photogenerated electrons reduce Co(III) to Co(II), a step thermodynamically enabled by the relative positions of the TiO2 conduction band and the cobalt redox potential. The reduced cobalt species then traps the alkyl radical to form a cobalt(III)‐alkyl complex 45C. This intermediate undergoes light‐induced β‐hydride elimination to release the alkene product 46 and regenerate the cobalt hydride species, culminating in H2 evolution to close the catalytic cycle. This work elegantly merges heterogeneous photocatalysis with molecular metalloenzyme‐inspired catalysis, opening new avenues for sustainable olefin synthesis.

SCHEME 25.

SCHEME 25

Photocatalytic conversion of carboxylic acids to alkenes by a TiO2 and cobaloxime dual catalyst system.

In a complementary approach that similarly exploits the synergy between heterogeneous photocatalysis and molecular cobalt catalysis, a distinct system based on Ag/TiO2 has been developed specifically for the valorization of fatty acid feedstocks. In 2025, Yang and colleagues reported a photocatalytic decarboxylative alkenylation strategy that merges heterogeneous Ag/TiO2 with a homogeneous cobaloxime cocatalyst, achieving the simultaneous and highly selective conversion of biomass‐derived fatty acids into linear α‐olefins (Scheme 26) [52]. In this mechanism, photogenerated holes on the TiO2 surface initiate the oxidation of the fatty acid to trigger decarboxylation. Crucially, the resulting alkyl radicals exhibit weak adsorption on the Ag nanoparticles, allowing them to rapidly desorb and diffuse into the solution to be intercepted by the Co(II) complex, forming Co(III)–alkyl intermediates. Subsequent β‐hydride elimination selectively yields the α‐olefin product, while the photogenerated electrons facilitate the regeneration of the cobalt catalyst and the concomitant evolution of H2. The low binding affinity of the Ag cocatalyst toward radical intermediates is pivotal, as it effectively suppresses competing hydrogenation and coupling side reactions, resulting in α‐olefin selectivity as high as 96%. This hybrid strategy provides a mild and recyclable platform for the high‐value production of α‐olefins from renewable fatty acid resources.

SCHEME 26.

SCHEME 26

Ag/TiO2–cobaloxime hybrid photocatalytic system for decarboxylative alkenylation of fatty acids to linear α‐olefins.

2.4. Electrochemical Decarboxylative Elimination for Alkene Preparation

Electrochemistry provides a distinctively sustainable approach to redox transformations, employing electrons as non‐traceable reagents and frequently obviating the necessity for stoichiometric oxidants/reductants [53, 54, 55, 56, 57]. Since the pioneering Kolbe electrolysis [58], electrochemical methods have evolved significantly, providing complementary and often advantageous pathways for decarboxylative reactions. By directly interfacing organic synthesis with renewable electricity, these strategies align with green chemistry principles and present promising avenues for scalable synthesis of olefins under mild conditions. This section highlights recent key advances in this burgeoning field.

A pivotal development was reported by Baran and colleagues in 2023, who devised an innovative method distinct from classical Hofer–Moest‐type substitution [59]. They postulated that the carbocation intermediate could undergo proton elimination to directly form an alkene. Realizing this concept, they achieved a direct, single‐step conversion of carboxylic acids to alkenes using alternating current electrolysis (ACE), a process entirely free of metals (Scheme 27) [60]. Their key finding was that ACE, in which electrode polarity switches at a constant frequency, was crucial for the transformation, as direct current electrolysis failed to yield the product. The periodic polarity inversion effectively mitigates electrode fouling and suppresses localized acidification, thereby preserving the operational robustness of the system. The addition of pivalic acid (PivOH) as a sacrificial additive prevented oxidative degradation of the alkene products. Remarkably, this mild protocol was successfully demonstrated on a kilogram scale, underscoring its practical potential for efficient and environmentally friendly alkene synthesis.

SCHEME 27.

SCHEME 27

Electrochemical decarboxylative elimination driven by alternating polarity.

Also in 2023, Zhang and co‐workers presented a complementary green and metal‐free electrochemical strategy (Scheme 28) [61]. Their system employed inexpensive carbon felt as both cathode and anode, operating at room temperature under a constant potential of 2.5 V in acetonitrile with n Bu4NOAc as the electrolyte. This setup enabled the highly selective conversion of a broad range of carboxylic acids to their corresponding alkenes. A plausible mechanism involves anodic oxidation of the carboxylate anion 49A to a radical species 49B, which undergoes rapid decarboxylation. The resulting carbon‐centered radical 49C is further oxidized, likely forming a cationic intermediate 49D that eliminates a proton to furnish the olefin 50a. Concurrent cathodic reduction regenerates acetate from acetic acid with H2 evolution. The simple, mild conditions and sole use of electricity as the driving force highlight the appeal of this method.

SCHEME 28.

SCHEME 28

Electrochemical decarboxylative elimination using direct current.

Beyond modulating current or potential, the strategic design of the electrochemical environment itself can control selectivity. Recognizing the profound influence of supporting electrolytes, Nozaki and colleagues developed in 2025 a method where tetraalkylphosphonate anions were employed to stabilize primary carbocation intermediates in situ (Scheme 29) [62]. Under electrolysis using carbon and platinum electrodes, the carboxylate substrate is oxidatively decarboxylated. The resulting transient primary carbocation is effectively stabilized through non‐covalent interactions with the strongly donating (nBuO)2PO2 anion from the electrolyte, Me4N+( n BuO)2PO2 . This stabilization suppresses competing isomerization pathways, enabling the highly selective formation of terminal α‐olefins upon deprotonation. This work elegantly demonstrates how electrolyte engineering can be leveraged to steer reactive intermediates toward desired products with high fidelity.

SCHEME 29.

SCHEME 29

Electrochemical decarboxylation elimination using Me4N+( n BuO)2PO2 as the supporting electrolyte.

The recent contributions from the Baran, Zhang, and Nozaki groups have significantly elevated the status of electrochemical methods from a laboratory curiosity to a viable synthetic tool. Baran's implementation of alternating current electrolysis (ACE) represents a milestone in addressing electrode fouling, while Nozaki's electrolyte‐mediated approach demonstrates exquisite control over carbocation stabilization to prevent unintended isomerization. However, a persistent limitation in current electrochemical protocols is the substrate scope, specifically the compatibility with sensitive polar functional groups or electron‐rich motifs that are prone to anodic over‐oxidation. When evaluating industrial potential, electrochemical systems can be effectively scaled by increasing electrode surface area or transitioning to continuous‐flow cell configurations. Addressing these interfacial and compatibility challenges provides a more robust foundation for the broader adoption of electrocatalytic decarboxylative elimination.

3. Summary and Outlook

The direct elimination of carboxylic acids to olefins has evolved into a multi‐faceted research landscape, driven by foundational contributions from major research teams. The Tolman group has pioneered noble‐metal‐catalyzed protocols for the valorization of biomass‐derived fatty acids, establishing the benchmark for high‐turnover systems. Concurrently, the Tunge group has expanded the synthetic utility of this transformation to complex enamides through innovative photocatalytic and synergistic dual‐catalytic strategies. More recently, the emergence of electrochemical methods by the Baran and other groups has introduced a sustainable alternative that leverages electricity as a traceless redox agent.

A comparative assessment of current activation modes reveals distinct trade‐offs in greenness, cost, and scalability. While thermal induction is technically simple and scalable, its reliance on harsh conditions and stoichiometric oxidants like hypervalent iodine limits its “green” profile. Transition‐metal catalysis offers high precision, and the recent shift toward noble‐metal‐free systems (using Ni, Cu, or Fe) and green solvents (such as γ‐valerolactone, GVL) has significantly improved its sustainability and reduced costs. Photocatalysis excels in functional group tolerance under mild conditions but faces high costs for iridium‐based sensitizers and engineering bottlenecks in light penetration. Electrochemistry stands out as the most promising regarding atom economy and energy efficiency; however, it is currently the most restricted in terms of substrate scope for polar molecules.

Despite this progress, several core bottlenecks persist as critical hurdles for future research. First, regioselectivity control, particularly the consistent production of terminal α‐olefins without isomerization, remains challenging in long‐chain substrates. Second, the sustainability of activating reagents is a concern; many protocols still require stoichiometric acid anhydrides or SO2F2, necessitating the development of catalysts capable of direct ─COOH activation. Third, catalyst recovery and electrode passivation are paramount for industrial viability. Future efforts should prioritize the development of heterogeneous or recyclable bifunctional catalysts to simplify downstream separation. For electrochemical systems, moving beyond trial‐and‐error to adopt process intensification through flow chemistry will be essential to mitigate electrode fouling. By addressing these specific challenges, the decarboxylative elimination of carboxylic acids is poised to transition from an elegant laboratory methodology to a cornerstone technology for sustainable chemical manufacturing.

Author Contributions

Yi Zhou and Zhanzhou Wei were responsible for identifying and selecting relevant literature and drafting the manuscript. Yabing Zhang, Yunfei Zhang, and Kehan He contributed to the conceptualization, review, and final editing of the manuscript.

Conflicts of Interest

The authors declare no conflicts of interest.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 22101299), Chinese Universities Scientific Fund (No. 2025TC055), 2025 China Agricultural University‐Xichang University Joint Research Fund Project (No. ZXL202502) and the Open Research Fund of Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University.

In this work, the authors used DeepSeek‐3.2 (accessed December 2025) to organize the Introduction section for improved clarity and flow. All AI‐generated suggestions were reviewed, revised, and approved by the authors, who confirm the accuracy and integrity of the results and take full responsibility for the originality and integrity of the work.

Biographies

Yi Zhou is currently an undergraduate student at the College of Science, China Agricultural University. He is studying under Professor Yunfei Zhang and is currently interested in transition metal‐catalyzed decarboxylation.

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Zhanzhou Wei is currently an undergraduate student at the College of Science, China Agricultural University. He is studying under Professor Yunfei Zhang and is currently interested in electrochemical decarboxylation.

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Yabing Zhang received his bachelor's degree (2013) from Beijing University of Chemical Technology, master's degree (2016) from the Institute of Process Engineering, Chinese Academy of Sciences, and Ph.D. (2022) from Tsinghua University. He joined the College of Science, China Agricultural University (2024). He has published research articles as the first author or corresponding author in journals such as ACS Sustainable Chemistry & Engineering, Surfaces and Interfaces, Applied Surface Science, and Langmuir. His current research interests include smart responsive materials, transition metal catalysis, and nano‐pesticide carriers.

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Yunfei Zhang received his B.S. degree (2013) from China Agricultural University and received his Ph.D. degree (2018) under the supervision of Prof. Zhangjie Shi at Peking University. After postdoctoral research (2018‐2020) with Tristan Lambert at Cornell University, he joined the College of Science at China Agricultural University (2020). He has published his research works as the first author or corresponding author in journals such as Acc. Chem. Res., Angew. Chem. Int. Ed., ACS Catal., Org. Lett., and J. Org. Chem. His current research interests include electrochemical organic synthesis, transition metal catalysis, exploration of novel pesticides, and so on.

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Kehan He received his B.S. degree (2010) from Xichang University, and received his Ph.D. degree (2018) under the supervision of Prof. Yang Li at Xi'an Jiaotong University. Afterward, he joined the College of Science at Xichang University (2019). He has published his research works as the first author or corresponding author in journals such as Angew. Chem. Int. Ed., Org. Lett., and ChemSusChem. His current research interests include photochemistry, transition‐metal catalysis, and so on.

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Contributor Information

Yabing Zhang, Email: ybzhang@cau.edu.cn.

Yunfei Zhang, Email: zyfeichem@cau.edu.cn.

Kehan He, Email: hdss2006@163.com.

Data Availability Statement

Data sharing is not applicable to this article as no new data were created or analyzed in this study.

References

  • 1. Cueny E. S., Nieszala M. R., Froese R. D., and Landis C. R., “Nature of the Active Catalyst in the Hafnium‐Pyridyl Amido‐Catalyzed Alkene Polymerization,” ACS Catalysis 11 (2021): 4301–4309, 10.1021/acscatal.1c00394. [DOI] [Google Scholar]
  • 2. Wang J., Wang Y., Liang Y., Zhou L., Liu L., and Zhang Z., “Late‐Stage Modification of Drugs via Alkene Formal Insertion Into Benzylic C−F Bond,” Angewandte Chemie International Edition 62 (2023): e202215062, 10.1002/anie.202215062. [DOI] [PubMed] [Google Scholar]
  • 3. Camarca M., Heuett W., and Jaber D., “CHEMCompete‐II: An Organic Chemistry Card Game To Differentiate Between Substitution and Elimination Reactions of Alcohols,” Journal of Chemical Education 96 (2019): 2535–2539, 10.1021/acs.jchemed.9b00486. [DOI] [Google Scholar]
  • 4. Fu Z., Li Z., Song Y., Yang R., Liu Y., and Cai H., “Decarboxylative Halogenation and Cyanation of Electron‐Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron‐Rich Ones Through Pd Catalyst Under Aerobic Conditions,” The Journal of Organic Chemistry 81 (2016): 2794–2803, 10.1021/acs.joc.5b02873. [DOI] [PubMed] [Google Scholar]
  • 5. Fu Z., Jiang Y., Wang S., Song Y., Guo S., and Cai H., “Pd‐Catalyzed Decarboxylative Ortho ‐Halogenation of Aryl Carboxylic Acids With Sodium Halide NaX Using Carboxyl as a Traceless Directing Group,” Organic Letters 21 (2019): 3003–3007, 10.1021/acs.orglett.9b00460. [DOI] [PubMed] [Google Scholar]
  • 6. Chatterjee A., Hopen Eliasson S. H., and Jensen V. R., “Selective Production of Linear α‐olefins via Catalytic Deoxygenation of Fatty Acids and Derivatives,” Catalysis Science & Technology 8 (2018): 1487–1499, 10.1039/C7CY02580G. [DOI] [Google Scholar]
  • 7. Zhang X., Jordan F., and Szostak M., “Transition‐metal‐catalyzed Decarbonylation of Carboxylic Acids to Olefins: Exploiting Acyl C–O Activation for the Production of High Value Products,” Organic Chemistry Frontiers 5 (2018): 2515–2521, 10.1039/C8QO00585K. [DOI] [Google Scholar]
  • 8. Pan‐Pan Gao W.‐J. X. and Chen J.‐R., “Recent Progresses in Visible‐Light‐Driven Alkene Synthesis,” Chinese J Org Chem 42 (2022): 3923–3943. [Google Scholar]
  • 9. Deng C.‐Q. and Deng J., “Advances of the Past 12 Years in Decarboxylation of Biomass Carboxylic Acids to Biofuels and High‐value Chemicals via Photo‐ or Electrocatalysis,” Green Chemistry 27 (2025): 275–292, 10.1039/D4GC04788E. [DOI] [Google Scholar]
  • 10. Bacha J. D. and Kochi J. K., “Alkenes From Acids by Oxidative Decarboxylation,” Tetrahedron 24 (1968): 2215–2226, 10.1016/0040-4020(68)88124-4. [DOI] [Google Scholar]
  • 11. Huang H., Zhang G., and Chen Y., “Dual Hypervalent Iodine(III) Reagents and Photoredox Catalysis Enable Decarboxylative Ynonylation Under Mild Conditions,” Angewandte Chemie International Edition 54 (2015): 7872–7876, 10.1002/anie.201502369. [DOI] [PubMed] [Google Scholar]
  • 12. Wu S.‐W., Liu J.‐L., and Liu F., “Metal‐Free Microwave‐Assisted Decarboxylative Elimination for the Synthesis of Olefins,” Organic Letters 18 (2016): 1–3, 10.1021/acs.orglett.5b03069. [DOI] [PubMed] [Google Scholar]
  • 13. Foglia T. and Barr P., “Decarbonylation Dehydration of Fatty Acids to Alkenes in the Presence of Transition Metal Complexes,” Journal of the American Oil Chemists' Society 53 (1976): 737–741, 10.1007/BF02635473. [DOI] [Google Scholar]
  • 14. Miller J. A., Nelson J. A., and Byrne M. P., “A Highly Catalytic and Selective Conversion of Carboxylic Acids to 1‐alkenes of One Less Carbon Atom,” The Journal of Organic Chemistry 58 (1993): 18–20, 10.1021/jo00053a008. [DOI] [Google Scholar]
  • 15. Gooßen L. J. and Rodríguez N., “A Mild and Efficient Protocol for the Conversion of Carboxylic Acids to Olefins by a Catalytic Decarbonylative Elimination Reaction,” Chemical Communications 40 (2004): 724–725. [DOI] [PubMed] [Google Scholar]
  • 16. Le Nôtre J., Scott E. L., Franssen M. C., and Sanders J. P., “Selective Preparation of Terminal Alkenes From Aliphatic Carboxylic Acids by a Palladium‐Catalysed Decarbonylationelimination reaction,” Tetrahedron Letters 51 (2010): 3712–3715. [Google Scholar]
  • 17. Miranda M. O., Pietrangelo A., Hillmyer M. A., and Tolman W. B., “Catalytic Decarbonylation of Biomass‐Derived Carboxylic Acids as Efficient Route to Commodity Monomers,” Green Chemistry 14 (2012): 490, 10.1039/c2gc16115j. [DOI] [Google Scholar]
  • 18. Ortuño M. A., Dereli B., and Cramer C. J., “Mechanism of Pd‐Catalyzed Decarbonylation of Biomass‐Derived Hydrocinnamic Acid to Styrene Following Activation as an Anhydride,” Inorganic Chemistry 55 (2016): 4124–4131, 10.1021/acs.inorgchem.5b02664. [DOI] [PubMed] [Google Scholar]
  • 19. Chatterjee A., Hopen Eliasson S. H., Törnroos K. W., and Jensen V. R., “Palladium Precatalysts for Decarbonylative Dehydration of Fatty Acids to Linear Alpha Olefins,” ACS Catalysis 6 (2016): 7784–7789, 10.1021/acscatal.6b02460. [DOI] [Google Scholar]
  • 20. Dawes G. J. S., Scott E. L., Le Nôtre J., Sanders J. P., and Bitter J. H., “Deoxygenation of Biobased Molecules by Decarboxylation and Decarbonylation—A Review on the Role of Heterogeneous, Homogeneous and Bio‐Catalysis,” Green Chemistry 17 (2015): 3231–3250, 10.1039/C5GC00023H. [DOI] [Google Scholar]
  • 21. Hopen Eliasson S. H., Chatterjee A., Occhipinti G., and Jensen V. R., “Green Solvent for the Synthesis of Linear α‐Olefins From Fatty Acids,” ACS Sustainable Chemistry & Engineering 7 (2019): 4903–4911, 10.1021/acssuschemeng.8b05523. [DOI] [Google Scholar]
  • 22. Guan C., Qi H., Han L., Zhang G., Lyu J., and Ding C., “An Efficient Platform for Decarboxylative Functionalization of Carboxylic Acids Using Sulfuryl Fluoride: Pd‐catalyzed Decarboxylative Dehydrogenation of Alkanecarboxylic Acids and Decarboxylative Cross‐coupling of Arenecarboxylic Acids,” Organic Chemistry Frontiers 11 (2024): 4156–4167, 10.1039/D4QO00428K. [DOI] [Google Scholar]
  • 23. Maetani S., Fukuyama T., Suzuki N., Ishihara D., and Ryu I., “Efficient Iridium‐Catalyzed Decarbonylation Reaction of Aliphatic Carboxylic Acids Leading to Internal or Terminal Alkenes,” Organometallics 30 (2011): 1389–1394, 10.1021/om1009268. [DOI] [Google Scholar]
  • 24. Ternel J., Lebarbé T., Monflier E., and Hapiot F., “Catalytic Decarbonylation of Biosourced Substrates,” Chemsuschem 8 (2015): 1585–1592, 10.1002/cssc.201500214. [DOI] [PubMed] [Google Scholar]
  • 25. Zhao J.‐F., Duan X.‐H., Gu Y.‐R., Gao P., and Guo L.‐N., “Iron‐Catalyzed Decarboxylative Olefination of Cycloketone Oxime Esters With α,β‐Unsaturated Carboxylic Acids via C–C Bond Cleavage,” Organic Letters 20 (2018): 4614–4617, 10.1021/acs.orglett.8b01901. [DOI] [PubMed] [Google Scholar]
  • 26. John A., Miranda M. O., Ding K., et al., “Nickel Catalysts for the Dehydrative Decarbonylation of Carboxylic Acids to Alkenes,” Organometallics 35 (2016): 2391–2400, 10.1021/acs.organomet.6b00415. [DOI] [Google Scholar]
  • 27. Gao P., Wu H., Yang J.‐C., and Guo L. N., “Iron‐Catalyzed Decarboxylative Olefination of Unstrained Carbon–Carbon Bonds Relying on Alkoxyl Radical Induced Cascade,” Organic Letters 21 (2019): 7104–7108, 10.1021/acs.orglett.9b02675. [DOI] [PubMed] [Google Scholar]
  • 28. Maetani S., Fukuyama T., Suzuki N., Ishihara D., and Ryu I., “Iron‐catalyzed Decarbonylation Reaction of Aliphatic Carboxylic Acids Leading to α‐olefins,” Chemical Communications 48 (2012): 2552, 10.1039/c2cc18093f. [DOI] [PubMed] [Google Scholar]
  • 29. Wu Y., Zhou Y., Tan K. B., et al., “Advanced Synthesis of Hierarchically Porous Zeolite Catalysts Utilizing Biomass Templates for the Catalytic Pyrolysis of Stearic Acid Into Short‐Chain Olefins,” ACS Applied Materials & Interfaces 16 (2024): 63455–63469, 10.1021/acsami.4c11403. [DOI] [PubMed] [Google Scholar]
  • 30. Tian J., Li J., Zhang M., et al., “Structural Isomerism in Ce‐MOFs Directs Ni/CeO2 Catalyst Design for Selective Fatty Acid Deoxygenation to Linear α‐olefins,” Chemical Communications 62 (2026): 493–496, 10.1039/D5CC05953D. [DOI] [PubMed] [Google Scholar]
  • 31. Wu Y., Wang Y., Wu J., et al., “Engineering of Zeolite Framework Aluminum Spatial Distribution Boosts Light Olefins Yield in Catalytic Pyrolysis of Fatty Acid,” ACS Sustainable Chemistry & Engineering 14 (2026): 4297–4309, 10.1021/acssuschemeng.6c00821. [DOI] [Google Scholar]
  • 32. John A., Dereli B. S., Ortuño M. A., et al., “Selective Decarbonylation of Fatty Acid Esters to Linear α‐Olefins,” Organometallics 36 (2017): 2956–2964, 10.1021/acs.organomet.7b00411. [DOI] [Google Scholar]
  • 33. John A., Hillmyer M. A., and Tolman W. B., “Anhydride‐Additive‐Free Nickel‐Catalyzed Deoxygenation of Carboxylic Acids to Olefins,” Organometallics 36 (2017): 506–509, 10.1021/acs.organomet.6b00940. [DOI] [Google Scholar]
  • 34. Stanton M. P. and Hoover J. M., “Copper‐Catalyzed Decarboxylative Elimination of Carboxylic Acids to Styrenes,” The Journal of Organic Chemistry 88 (2023): 1713–1719, 10.1021/acs.joc.2c02705. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 35. Cartwright K. C., Lang S. B., and Tunge J. A., “Photoinduced Kochi Decarboxylative Elimination for the Synthesis of Enamides and Enecarbamates From N ‐Acyl Amino Acids,” The Journal of Organic Chemistry 84 (2019): 2933–2940, 10.1021/acs.joc.9b00167. [DOI] [PubMed] [Google Scholar]
  • 36. Candish L., Standley E. A., Gómez‐Suárez A., Mukherjee S., and Glorius F., “Catalytic Access to Alkyl Bromides, Chlorides and Iodides via Visible Light‐Promoted Decarboxylative Halogenation,” Chemistry—A European Journal 22 (2016): 9971–9974, 10.1002/chem.201602251. [DOI] [PubMed] [Google Scholar]
  • 37. Constantin T., Zanini M., Regni A., Sheikh N. S., Juliá F., and Leonori D., “Aminoalkyl Radicals as Halogen‐atom Transfer Agents for Activation of Alkyl and Aryl Halides,” Science 367 (2020): 1021–1026, 10.1126/science.aba2419. [DOI] [PubMed] [Google Scholar]
  • 38. Brar D. S., Aponte R., and Tunge J., “Photoredox‐Catalyzed Decarboxylative Elimination via Halogen Atom Transfer,” The Journal of Organic Chemistry 90 (2025): 5274–5280, 10.1021/acs.joc.5c00237. [DOI] [PubMed] [Google Scholar]
  • 39. Crisenza G. E. M., Mazzarella D., and Melchiorre P., “Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes,” Journal of the American Chemical Society 142 (2020): 5461–5476, 10.1021/jacs.0c01416. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 40. Lima C. G. S., de M Lima T., Duarte M., Jurberg I. D., and Paixão M. W., “Organic Synthesis Enabled by Light‐Irradiation of EDA Complexes: Theoretical Background and Synthetic Applications,” ACS Catalysis 6 (2016): 1389–1407, 10.1021/acscatal.5b02386. [DOI] [Google Scholar]
  • 41. Chen K.‐Q., Shen J., Wang Z.‐X., and Chen X.‐Y., “A Donor–acceptor Complex Enables the Synthesis of E‐olefins From Alcohols, Amines and Carboxylic Acids,” Chemical Science 12 (2021): 6684–6690, 10.1039/D1SC01024G. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 42. Chan A. Y., Perry I. B., Bissonnette N. B., et al., “Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis,” Chemical Reviews 122 (2022): 1485–1542, 10.1021/acs.chemrev.1c00383. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 43. West J. G., Huang D., and Sorensen E. J., “Acceptorless Dehydrogenation of Small Molecules Through Cooperative Base Metal Catalysis,” Nature Communications 6 (2015): 10093, 10.1038/ncomms10093. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 44. Cartwright K. C. and Tunge J. A., “Decarboxylative Elimination of N ‐Acyl Amino Acids via Photoredox/Cobalt Dual Catalysis,” ACS Catalysis 8 (2018): 11801–11806, 10.1021/acscatal.8b03282. [DOI] [Google Scholar]
  • 45. Wei N. and Beil S. B., “Aryl Halide‐Driven Nickel Photocatalytic Decarboxylative Elimination,” ACS Catalysis 16 (2026): 5105–5114, 10.1021/acscatal.5c08828. [DOI] [Google Scholar]
  • 46. Tlahuext‐Aca A., Candish L., Garza‐Sanchez R. A., and Glorius F., “Decarboxylative Olefination of Activated Aliphatic Acids Enabled by Dual Organophotoredox/Copper Catalysis,” ACS Catalysis 8 (2018): 1715–1719, 10.1021/acscatal.7b04281. [DOI] [Google Scholar]
  • 47. Cheng W.‐M., Shang R., and Fu Y., “Irradiation‐induced Palladium‐Catalyzed Decarboxylative Desaturation Enabled by a Dual Ligand System,” Nature Communications 9 (2018): 5215, 10.1038/s41467-018-07694-w. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 48. Sun X., Chen J., and Ritter T., “Catalytic Dehydrogenative Decarboxyolefination of Carboxylic Acids,” Nature Chemistry 10 (2018): 1229–1233, 10.1038/s41557-018-0142-4. [DOI] [PubMed] [Google Scholar]
  • 49. Gisbertz S. and Pieber B., “Heterogeneous Photocatalysis in Organic Synthesis,” ChemPhotoChem 4 (2020): 456–475, 10.1002/cptc.202000014. [DOI] [Google Scholar]
  • 50. Li X., Peng Y., Huang Z., et al., “Combined Hydrogen and Alkane Production by Photocatalytic Decarboxylative C–C Homocoupling of Fatty Acid by Constructing a Hydrogen‐Deficient Catalytic Interface,” ACS Catalysis 14 (2024): 3675–3686, 10.1021/acscatal.3c06070. [DOI] [Google Scholar]
  • 51. Maruyama E., Jin X., and Nozaki K., “Photocatalytic Acceptorless Conversion of Carboxylic Acids, Aldehydes, and Alcohols to Alkenes by a TiO2 and Cobaloxime Dual‐Catalyst System,” The Journal of Organic Chemistry 90 (2025): 10416–10424, 10.1021/acs.joc.5c01153. [DOI] [PubMed] [Google Scholar]
  • 52. Li X., Xu H., Ku C., et al., “Photocatalytic Decarboxylative Alkenylation of Fatty Acids for Coproduction of Linear α‐Olefin and Hydrogen With High Selectivity,” ACS Catalysis 15 (2025): 19192–19204, 10.1021/acscatal.5c04570. [DOI] [Google Scholar]
  • 53. Rein J., Zacate S. B., Mao K., and Lin S., “A Tutorial on Asymmetric Electrocatalysis,” Chemical Society Reviews 52 (2023): 8106–8125, 10.1039/D3CS00511A. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 54. van der Ham M. P. J. M., Creus J., Bitter J. H., Koper M. T. M., and Pescarmona P. P., “Electrochemical and Non-Electrochemical Pathways in the Electrocatalytic Oxidation of Monosaccharides and Related Sugar Alcohols into Valuable Products,” Chemical Reviews 124 (2024): 11915–11961. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 55. Wang Y., Hu J., Zeng L., and Lei A., “Advancing Sustainable Chemistry Through Organic Electrosynthesis: A Perspective,” Science China Chemistry 69 (2025): 640–658, 10.1007/s11426-025-3006-x. [DOI] [Google Scholar]
  • 56. Xiong P. and Xu H.‐C., “Molecular Photoelectrocatalysis for Radical Reactions,” Accounts of Chemical Research 58 (2025): 299–311, 10.1021/acs.accounts.4c00739. [DOI] [PubMed] [Google Scholar]
  • 57. Zeng W., Wang Y., Peng C., and Qiu Y., “Organo‐mediator Enabled Electrochemical Transformations,” Chemical Society Reviews 54 (2025): 4468–4501, 10.1039/D4CS01142B. [DOI] [PubMed] [Google Scholar]
  • 58. Kolbe H., “Untersuchungen über die Elektrolyse Organischer Verbindungen,” Justus Liebigs Annalen der Chemie 69 (1849): 257–294, 10.1002/jlac.18490690302. [DOI] [Google Scholar]
  • 59. Leech M. C. and Lam K., “Electrosynthesis Using Carboxylic Acid Derivatives: New Tricks for Old Reactions,” Accounts of Chemical Research 53 (2020): 121–134, 10.1021/acs.accounts.9b00586. [DOI] [PubMed] [Google Scholar]
  • 60. Garrido‐Castro A. F., Hioki Y., Kusumoto Y., et al., “Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity,” Angewandte Chemie International Edition 62 (2023): e202309157, 10.1002/anie.202309157. [DOI] [PubMed] [Google Scholar]
  • 61. Yu J., Liu T., Sun W., and Zhang Y., “Electrochemical Decarboxylative Elimination of Carboxylic Acids to Alkenes,” Organic Letters 25 (2023): 7816–7821, 10.1021/acs.orglett.3c02997. [DOI] [PubMed] [Google Scholar]
  • 62. Ito T., Jin X., and Nozaki K., “Electrochemical Conversion of Carboxylic Acids to Terminal Alkenes Enabled by Dialkyl Phosphate Electrolyte,” Tetrahedron 176 (2025): 134560, 10.1016/j.tet.2025.134560. [DOI] [Google Scholar]

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Data sharing is not applicable to this article as no new data were created or analyzed in this study.


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