A General Strategy for the Synthesis of Jerangolids Enabled by π‐allyl Stille Coupling

Janick Schug; Bernd Morgenstern; Johann Jauch

doi:10.1002/chem.70928

. 2026 Apr 6;32(23):e70928. doi: 10.1002/chem.70928

A General Strategy for the Synthesis of Jerangolids Enabled by π‐allyl Stille Coupling

Janick Schug ¹, Bernd Morgenstern ², Johann Jauch ^1,^✉

PMCID: PMC13282915 PMID: 41940694

ABSTRACT

Jerangolids are polyketide natural products with potent antifungal activity and low mammalian toxicity, originally isolated from Sorangium cellulosum So ce 307. Their structure, consisting of a δ‐lactone and a pyran unit connected by a chiral skipped 1,4‐diene, presents a significant synthetic challenge. Herein, we describe a general, modular strategy that enables the synthesis of all naturally occurring jerangolids and their stereoisomers, including the still elusive jerangolid H. The lactone fragment was built through a vinylogous Mukaiyama aldol reaction, with the hydroxymethyl group at C2 introduced in one step by Stille coupling with a novel p‐methoxybenzyloxymethyl (PMBM) stannatrane. The stereocenter at both C14 and C15 was generated via deoxygenation of a tertiary alcohol involving a [1,2]‐H‐shift. Using a highly modular approach recently developed by our group, the jerangolid framework was assembled in a single step through enantioselective π‐allyl Stille coupling of the two key fragments. Synthesis and comparison of both C14 epimers allowed us to unambiguously establish the total configuration of jerangolid H.

Keywords: [1,4]‐anionotropic alkynyl shift; jerangolid; stannatrane; total synthesis; π‐allyl Stille coupling

A general strategy for the synthesis of jerangolids is established, featuring a late‐stage π‐allyl Stille coupling of two advanced, highly customizable building blocks to form the skipped diene core. The approach provides access to all naturally occurring jerangolids, including jerangolid H, whose configuration is confirmed by NMR analysis.

1. Introduction

Jerangolids are a class of polyketides first isolated in 1995 by Höfle et al. from the myxobacterium Sorangium cellulosum So ce 307 [1, 2]. Their structure features a chiral 1,4‐skipped diene connected to a δ‐lactone and a pyran substituent (Figure 1). They share a major part of their structural motif, which is assumed to be the pharmacophore responsible for biological activity, with the ambruticins, another class of polyketides first isolated from Polyangium cellulosum var. fulvum and S. cellulosum So ce 10 by Strandtmann et al. [3, 4, 5, 6, 7, 8, 9]. Similar to ambruticins, jerangolids display potent antifungal activity against a variety of pathogens, including Mucor hiemalis, Trichosporon terrestre, and Trichoderma hamata with minimal inhibitory concentrations (MIC) in the range of 0.07–7.0 mg mL⁻¹ [2]. Both classes target the high osmolarity glycerol (HOG) signaling pathway in histidine kinase 1 (Hik1) expressing cells, leading to an intracellular accumulation of free fatty acids and glycerol, ultimately resulting in cell death [10, 11, 12, 13, 14]. Since this pathway is absent in mammals, jerangolids represent promising candidates for the development of novel antifungal drugs due to their remarkably low toxicity.

Structure of all naturally occurring jerangolids and ambruticins with the supposed pharmacophore marked in red.

To date, total syntheses of all naturally occurring jerangolids, except jerangolid H (3), including some truncated analogues [15, 16, 17, 18], have been reported [19, 20, 21, 22]. Markó et al. achieved the first synthesis of jerangolid D (4) in 22 steps with a 6.1% yield in the longest linear sequence (LLS) [19]. Hanessian et al. subsequently synthesized jerangolid A (5, 23 steps, 1.9% LLS) [20], followed by Hahn et al. with jerangolid E (2, 23 steps, 4.0% LLS) [21], and most recently, our group completed the synthesis of jerangolid B (1, 20 steps, 5.7% LLS) [22].

While previous strategies relied on olefination reactions to construct the skipped diene core from three building blocks, we have recently shown that this motif can be accessed in a single step via enantioselective sp³–sp² Stille coupling (Scheme 1) [22]. We envisioned that our strategy could also be applicable to the synthesis of all jerangolids, including the still elusive jerangolid H (3).Retrosynthetically, the jerangolids can be disconnected at C8‐C9 to a trifluoroacetate 12 and a vinylstannane 13. For the synthesis of Jerangolid A (5) and H (3), we planned to install the hydroxymethyl group at C2 in 12 in a single step as a PMB‐protected ether via homologation of an α‐iodolactone through Stille coupling. The stereocenter at C14 required for jerangolid E (2) and H (3) can be generated by deoxygenation of the corresponding tertiary alcohol previously employed in our synthesis of jerangolid B (1). The olefin at C13–C14 required for Jerangolid A (5) and D (4) can be accessed through a Kochi‐Fürstner coupling of the corresponding vinyl triflate, obtained from an earlier intermediate within the same strategy. This ultimately leads to the same starting materials L‐(−)‐lactate (14) and 5‐trimethylsilyl‐pent‐4‐yn‐1‐ol (15) for all the here‐mentioned jerangolids.

SCHEME 1 — Retrosynthetic analysis of the jerangolids.

2. Results and Discussion

Construction of the lactone building block started from the aldehyde 16, which was synthesized in four steps starting from L‐(−)‐lactate (14) in 82% yield as previously described (Scheme 2) [22, 23]. Next, the aldehyde 16 was subjected to vinylogous Mukaiyama aldol reaction (VMAR) [24]. We found that silylketene acetal 18, lacking the methyl substituent at C2, delivered the desired allylic alcohol 20 in 86% yield with a highly improved diastereoselectivity of 95:5 compared to 17, delivering 19 in only 90:10 dr [22]. As previously discussed [22], the aldehyde forms a mismatched pair with R‐(BINOL), which reduces overall stereoselectivity. The additional decrease observed for the C2‐substituted silylketene acetal likely stems from steric interactions between its methyl group and the chiral ligand. These results indicate that C2‐substituted silylketene acetals are generally challenging substrates for this reaction class.

SCHEME 2 — Synthesis of lactone 25 and p‐methoxybenzyloxy methyl stannatrane 28 (for details see Supporting Information).

Subsequent one‐pot sequence of cyclisation with K₂CO₃ in MeOH and methylation with Me₂SO₄ in acetone delivered the desired lactone 21 in 91% yield [25]. For the synthesis of Jerangolid A (5) and H (3), we initially planned to introduce the hydroxymethyl group at C2 via halogen‐metal exchange and reaction with formaldehyde, first employed by Hanessian et al. [20] α‐Iodination afforded the vinyl iodide 22 in 74% yield. Unfortunately, even after extensive experimentation, subsequent halogen‐metal exchange and reaction with freshly cracked formaldehyde delivered the desired α‐hydroxymethyl lactone 23 in only 20% yield, with the main product being the dehalogenated lactone 21 [26]. Further attempts to introduce the PMB group using PMBCl/Ag₂O at 50°C in DMF or Dudley reagent II resulted in complete decomposition of the starting material [27, 28], likely due to the inherent instability of the lactone fragment under either basic or Lewis acidic conditions [29, 30, 31, 32] Because of this instability, protecting the hydroxymethyl group as a PMB ether was crucial, as this is one of the few groups that can be cleaved orthogonally under neutral conditions using DDQ. We therefore had to devise a strategy that allows us to introduce a p‐methoxybenzyloxy methyl (PMBM) group in a single step.

Our initial attempt to introduce the PMBM group via Stille coupling of 22 using tributyl[(4‐methoxyphenyl)methyl] stannane resulted either in no conversion or complete decomposition (Table 1, entries 1 and 2) [33, 34, 35, 36]. As α‐alkoxy stannanes are known to transmetallate only sluggishly [37], we reasoned that this step in the catalytic cycle was inhibited. In such cases, the transmetallation rate can often be enhanced by the addition of fluoride salts [38, 39], which generate a pentacoordinated tin species, thereby weakening the Sn─C bond [40, 41]. However, the addition of 2.0 equiv. of KF resulted in complete decomposition of the starting material, most likely due to side reactions involving the TBS ether (Table 1, entry 2).

TABLE 1.

Optimization for the synthesis of lactone 24 via Stille coupling (see Table 1) ^a (for details see Supporting Information).

	Conditions ^a	Yield (%) 24 (21) ^b
1 ^c	5 mol% Pd(PPh₃)₄, 10 mol% CuI, THF, 80°C, 45 min	‐ ^d
2 ^c	5 mol% Pd(PPh₃)₂Cl₂, 2.0 equiv. KF, THF, 74°C, 30 min	‐ ^e
3	5 mol% Pd(PPh₃)₄, THF, 66°C, 30 min	36 (18)
4	5 mol% Pd(dppf)Cl₂, THF, 66°C, 30 min	34 (13)
5	5 mol% [(η³‐C₃H₅)PdCl]₂, 40 mol% PCy₃, toluene, 60°C, 10 min	50 (18)
6	5 mol% [(η³‐C₃H₅)PdCl]₂, 20 mol% tBu₂MePHBF₄, toluene, 58°C, 10 min	‐ ^e
7	5 mol% [(η³‐C₃H₅)PdCl]₂, 20 mol% Ad₃P, toluene, 60°C, 10 min	39 (22)
8	5 mol% [(η³‐C₃H₅)PdCl]₂, 20 mol% Ad₂ nBuP, toluene, 58°C, 10 min	82 (6)

Open in a new tab

^{^a}

Reactions were performed in a microwave at a 0.25–1.00 mmol scale using 1.1 equiv. of p‐methoxybenzyl methyl stannatrane (28).

^{^b}

Yield of 21 was determined via 1H‐NMR.

^{^c}

Tributyl[(4‐methoxyphenyl)methyl] stannane was used instead [33, 34, 35, 36].

^{^d}

No reaction occurred.

^{^e}

Complete decomposition of lactone 22.

An alternative strategy to selectively weaken the Sn─C bond and therefore improve the transmetallation rate is achieved by internal coordination using stannatranes (Scheme 2) [42, 43, 44, 45, 46, 47, 48]. In their seminal work, Vedejs et al. demonstrated that even alkyl groups, which are typically the most challenging substrates, can be selectively transmetallated under mild conditions [44, 49]. The required stannatrane 28 was generated in two steps starting from commercial 5‐chloro‐1‐aza‐5‐stannabicyclo[3.3.3.]undecane (26). Iodomethylation with CH₂I₂ and Et₂Zn furnished 27 in 98% yield, and subsequent reaction with PMBOH using KH delivered stannatrane 28 in 75% yield as a crystalline solid [50, 51].

Stille coupling of vinyl iodide 22 using stannatrane 28 and 5 mol% Pd(PPh₃)₄ under microwave irradiation afforded the desired lactone, albeit in only 36% yield, accompanied by substantial amounts of 21 as a side product (Table 1, entry 3). Changing to Pd(dppf)Cl₂ led to similar results (Table 1, entry 4). As the vinyl iodide 22 itself is a difficult substrate owing to the high electron density at C2, we concluded that under these conditions, the rate‐limiting step is no longer the transmetallation but the oxidative addition. Consequently, strongly donating ligands such as trialkylphosphines are expected to accelerate the oxidative addition step [52], thereby increasing yields. Sterically demanding phosphine ligands are also able to lower the energy barrier of the reductive elimination by promoting the formation of a three‐coordinate Pd species (53, 54, 55).

As anticipated, switching to 5 mol% [(η³‐C₃H₅)PdCl]₂ together with 40 mol% PCy₃ as a sterically demanding, electron‐rich ligand in toluene increased yields to an acceptable 50% (Table 1, entry 5). Using toluene as a solvent provided the additional advantage that the formed stannatrane iodide side product crystallized out of solution at room temperature and could be recovered in near‐quantitative yield via simple filtration, while also serving as a convenient indicator of reaction progress. By further increasing sterical demand, we were able to identify Ad₂ nBuP as the optimal ligand affording the desired lactone 24 in an exceptional 82% yield (Table 1, entry 8). Any further increase in sterical demand, such as in the use of Ad₃P or tBu₂MePHBF₄, proved to be detrimental, leading to either decreased yield or complete decomposition (Table 1, entries 6 and 7) [56]

Deprotection of compound 24 had to be done using Pyr•HF, as even slightly Lewis acidic conditions, such as 2 mol% of Bi(OTf)₃ in water/MeCN, additionally led to the formation of PMB cleaved product [57]. Final trifluoroacylation delivered the desired lactone 25 in 74% yield over two steps (Scheme 2).

Next, we turned our focus to the synthesis of the pyrane building block for Jerangolid A (2) and D (3) (Scheme 3). The synthesis started with the preparation of alkene 29 in two steps from commercially available 5‐trimethylsilyl‐pent‐4‐yn‐1‐ol (15), as previously described by our group [18, 22]. Enantioselective epoxidation with the L‐fructose‐derived L‐Shi catalyst 31 afforded epoxide 30 in 75% yield (er = 96.5:3.5) [58, 59]. Subsequent Dess‐Martin oxidation and Carreira alkynylation with TMS acetylene and (+)‐NME [60, 61], with the aldehyde being added slowly over 10 h, provided the corresponding propargylic alcohol in a 10:1 dr. Intramolecular BF₃•OEt₂ catalyzed 6‐endo‐tet epoxide opening delivered pyrane 33 as a single diastereomer in 64% yield after chromatographic purification. For further discussion of this epoxide opening reaction, see our previous paper [22].

To install the C14 methyl‐substituted alkene, both TMS groups had to be cleaved first while the C14 hydroxy group was still present, as deprotection at C15 does not proceed without the adjacent OH group [62]. Therefore, stepwise deprotection delivered the secondary alcohol 34 in 87% yield. Subsequent double TMS protection and selective alcohol deprotection sequence then provided the TMS‐protected alkyne 35 in near‐quantitative yield. A two‐step sequence comprising oxidation to ketone and selective deprotonation at C13 with KHMDS, followed by reaction with PhNTf₂, delivered vinyltriflate 36 in 68% yield.

Attempts to couple vinyl triflate 37 with Me₂CuLi provided high conversion under various conditions, but were hardly reproducible, often furnishing chromatographically inseparable mixtures of 37 with an unsubstituted alkene side product. Best yield was achieved via Kochi–Fürstner coupling using MeMgBr and Fe(acac)₃ in a mixture of THF:NMP 10:1, providing alkene 37 in 89% yield [63, 64]. Subsequent deprotection and carbostannylation gave vinyl‐stannane 38 in 86% yield over two steps [65]

reproducible, often furnishing chromatographically inseparable mixtures of 37 with an unsubstituted alkene side product. Best yield was achieved via Kochi–Fürstner coupling using MeMgBr and Fe(acac)₃ in a mixture of THF:NMP 10:1, providing alkene 37 in 89% yield [63, 64]. Subsequent deprotection and carbostannylation gave vinyl‐stannane 38 in 86% yield over two steps [65].

The only building block left to be synthesized was the vinylstannane needed for the synthesis of Jerangolid E (2) and H (3) (Scheme 4). Synthesis began again with pyrane 33, in which the C14 methyl substituent was installed via a three‐step sequence comprising double TMS deprotection, oxidation to the ketone 39, and methyl addition following the procedure of Hatano et al. [66, 67, 68, 69], furnishing the tertiary alcohol 40 in quantitative yield as a separable 1.7:1 diastereomeric mixture.

To obtain the correct configuration at C14 in Jerangolid E (2) and H (3), the tertiary alcohol 40 had to be stereoselectively deoxygenated. As a tertiary carbenium is formed as an intermediate, the initial configuration at C14 was inconsequential in this step. Therefore, the epimeric mixture of 40 was reacted with BF₃•OEt₂ and Et₃SiH for 48 h at 40°C [70], providing a separable 6:1 mixture of C15 epimers 43 and 44 in 71% overall yield, with the desired product 45 only detected in trace amounts. The absolute configuration of both products was unambiguously confirmed by NOESY experiments. The formation of the C15 diastereomer 45 can be rationalized by the generation of the tertiary carbocation 41, which undergoes a [1,2]‐hydride shift to give the resonance‐stabilized oxacarbenium ion 42, which is then reduced by Et₃SiH from either face at C15, ultimately affording both epimers. This outcome turned out to be somewhat serendipitous, as it enabled the selective preparation of 14‐epi stannane 46 via subsequent carbostannylation in 96% yield.

In an effort to exploit the [1,2]‐hydride shift, we stereoselectively converted alkene 37 into the corresponding epoxide using L‐Shi catalyst 31, affording 47 in 64% yield and 10:1 dr (Scheme 5). In the presence of a Lewis acid, the epoxide 47 was expected to undergo Meinwald‐rearrangement, yielding a secondary alcohol upon reduction of the intermediate ketone. Subsequent deoxygenation of alcohol 48 would then furnish the desired compound.

SCHEME 5 — Attempted synthesis of pyrane 43 resulting in the [1,4]‐ alkynyl shift product 49 (for details see Supporting Information).

Accordingly, epoxide 47 was treated following the procedure described by Lebœuf et al. [71], with two equivalents of Et₃SiH and 5 mol % Bi(OTf)₃ in HFIP at 0°C for 20 min, affording 34% of the target compound 48 as a 2.4:1.0 mixture of its two C13 epimers after chromatography. The low selectivity with regard to the secondary alcohol 48 can be explained by stereospecific epoxide opening by Bi(OTf)₃, stereospecific 1,2‐Hydride shift from C13 to C14, and reduction of the resulting carbonyl group with low stereoselectivity to the secondary alcohol (Scheme 5).

In addition, 25% of an unknown crystalline compound was isolated and identified by x‐ray crystallography as an [1,4]‐alkynyl shift product 49, in which the alkynyl substituent originally attached to C11 had migrated to C14. The formation of product 49 can be rationalized mechanistically through protonation of epoxide 47 by the in situ‐generated trifluoromethanesulfonic acid, leading to the tertiary carbocation 50 (Scheme 5). The pyrane can then adopt a boat‐like conformation, allowing the nucleophilic α‐C in the TMS‐ethynyl group (α‐silyl effect) to attack the tertiary carbocation to form the TMS‐vinyl cation A, stabilized by the β‐silyl effect. A undergoes a 1,2‐silyl shift via intermediate B to yield the oxacarbocation 51. The latter is finally reduced by Et₃SiH to pyrane 49. Although, to the best of our knowledge, such a 1,4‐TMS ethinyl shift has not yet been described in the literature, the proposed mechanism is fully consistent with the known alpha and beta silyl effects and analogous reactions of vinylsilanes [72, 73, 74, 75, 76]. Due to their low tendency to migrate, such alkynyl shifts require either harsh conditions or prior alkyne activation, for example, by complexation with Au(III) or Co₂(CO)₈. [77, 78]. Notably, we observed this rearrangement exclusively in HFIP using Et₃SiH, with no reaction occurring even after 2 d when NaCNBH₃ or alternative solvents were used.

Attempts to perform the reaction of 47 to 48 with BF₃•OEt₂ and Et₃SiH in DCM at −78°C led to the formation of a dimeric side product. As no efficient means to prepare 48 could be found, this strategy was ultimately abandoned.

Despite this setback, we remained committed to the idea of exploiting the [1,2]‐hydride shift. The rapid hydride migration, likely responsible for the negligible formation of the desired product 45, suggested that deoxygenation of the S‐configured C15 epimer of 40 would allow us to obtain the correct configuration at C14. Reduction of the resulting oxacarbenium ion at C15 would then be expected to provide a separable mixture of both epimers. Accordingly, the required pyrane 52 was prepared in five steps starting from alkene 29 in 25% overall yield as a 1:2.6 diastereomeric mixture in an analogous way to 40 (Scheme 6). Subsequent deoxygenation provided the desired pyrane 45 almost exclusively, with an unexpectedly high diastereoselectivity of > 30:1 at C15. Final carbostannylation led to the stannane 53 in 88% yield.

SCHEME 6 — Synthesis of pyrane 45 and explanation for the encountered stereoselectivity (for details see Supporting Information).

This surprising and somewhat counterintuitive selectivity in the reduction of the oxacarbenium ion at C15 can be easily rationalized by the energy differences of the conformers formed in the transition state [79, 80]. After the [1,2]‐hydride shift, the oxacarbenium ion exists in a dynamic equilibrium between the two half‐chair conformations ³H₄ and ⁴H₃ [81]. According to the Curtin–Hammett principle, the position of this equilibrium is not expected to influence the diastereoselectivity, as the barrier for interconversion between conformers is low, allowing rapid equilibration. Hydride transfer from triethylsilane to the ³H₄ conformer from the Si face leads to an energetically favorable ⁴C₁ conformer in the transition state, in which the substituents at C14 and C11 occupy equatorial positions and steric interactions with the ethyl groups of the silane are minimized. In contrast, hydride transfer to the ⁴H₃ conformer from the Re face leads to an energetically less favorable ¹C₄ conformer in the transition state, as now both substituents are axial and additional steric repulsion arises between the alkynyl substituent at C11 and triethylsilane. The alternative twist‐boat transition states ²S_O and °S₂ , formed through Re attack on ³H₄ or Si attack on ⁴H₃ , respectively, are typically substantially higher in energy than the chair‐like transition states and are therefore not expected to contribute [80].

This would also explain the less pronounced diastereoselectivity observed for epimer 40. In this case, the methyl substituent would be axial at C14 in the ⁴C₁ conformer and equatorial in the ¹C₄ conformer. Although the ⁴C₁ conformer remains preferred due to the dominant steric repulsion of the alkynyl substituent at C11 with triethylsilane in the ¹C₄ conformer, the energy difference between these two transition states is expected to be significantly smaller, thus resulting in low stereoselectivity.

With all building blocks successfully synthesized, the stage was set for the π‐allyl Stille coupling (Scheme 7) [22, 82, 83, 84]. As discussed in our previous publication, the configuration at C8 is exclusively determined by the starting material, since epimerization of unsymmetrical 1,3‐disubstituted allylic substrates such as 25 via an η³–η¹–η³ pathway is not possible. In our case, inversion of configuration at C8 is expected, as transmetallation of the vinylstannane to the Pd(II) center occurs prior to C–C bond formation.

Both lactone 25 or 54 were coupled with either vinylstannane 46 or 53 using catalytic amounts of Pd₂dba₃ under pulsed microwave irradiation in a 2:1 mixture of THF and DMF (Scheme 7). This provided Jerangolid E (2) and 14‐epi Jerangolid E (55), as well as the OPMB‐protected jerangolid H 58 and 14‐epi Jerangolid H 56, in reproducible yields of 31%–33% after chromatographic purification. Cleavage of the PMB protecting group using DDQ in a 20:1 mixture of DCM and H₂O finally furnished jerangolid H (3) in 85% as well as 14‐epi jerangolid H (57) in near quantitative yield. By comparison of the NMR data of our synthetic 14‐epi‐jerangolid H (57) and jerangolid H (3) with those of natural jerangolid H (3), we could unambiguously prove that C14 is also S configured, as is the case for jerangolid E (2).

In the same manner, π‐allyl Stille coupling of either lactone 25 or 54 with vinylstannane 38 afforded jerangolid D (4) in 30% yield as well as jerangolid A (5) in 32% yield after deprotection using DDQ (Scheme 7).

3. Conclusion

In summary, we have demonstrated that the modular synthetic strategy previously developed for the synthesis of jerangolid B (1) is general and can be employed for the synthesis of all other naturally occurring jerangolids and stereoisomers thereof. Using this approach, we have successfully synthesized jerangolid A (5, 27 steps, 4.5% yield, 16 steps LLS), jerangolid D (4, 23 steps, 4.0% yield, 15 steps LLS), jerangolid E (2, 21 steps, 5.1% yield, 13 steps LLS), and jerangolid H (3, 24 steps, 4.8% yield, 14 steps LLS) as well as 14‐epi Jerangolid E (55) and 14‐epi Jerangolid H (57).

Key steps included the installation of the PMB protected hydroxymethyl group at C2 in a single step by Stille coupling using a novel p‐methoxybenzyloxymethyl (PMBM) stannatrane, formation of pyran 33 fragment through Carreira alkynylation of aldehyde 32 with subsequent cyclization, a stereoselective [1,2]‐H‐Shift generating both configurations at C14 and C15, the Kochi‐Fürstner coupling used for the synthesis of pyrane 37, and finally stereoselective π‐allyl Stille coupling of the respective building blocks to stereoselectively generate the chiral skipped diene core motif in a single step.

With this highly flexible strategy established, further work will focus on systematic derivatization of the jerangolid framework, particularly at C2, to enable comprehensive structure–activity relationship (SAR) studies and the development of a diverse jerangolid analog library.

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

Supporting Information: The authors have cited additional references within the Supporting Information [85, 86, 87, 88].

CHEM-32-e70928-s001.pdf^{(17.3MB, pdf)}

Acknowledgments

We thank Saarland University and the Deutsche Forschungsgemeinschaft (JA 616‐7/1; project number 280969177) for the continuous financial support of this project. We acknowledge the Service Center x‐ray Diffraction established with financial support from Saarland University and the Deutsche Forschungsgemeinschaft (INST 256/506‐1). We thank Dr. Klaus Hollemeyer and Kevin Staudt from the Service Center for Mass Spectrometry at Saarland University for recording HRMS data. Last but not least, we would like to express our sincere thanks to a reviewer for bringing the mechanistic possibility shown in Scheme 5 to our attention. In this regard, also helpful discussions with Prof. Dr. David Scheschkewitz are highly acknowledged.

Open access funding enabled and organized by Projekt DEAL.

This article is dedicated to Prof. Dr. Volker Schurig on the occasion of his 86^th birthday.

Data Availability Statement

The data that support the findings of this study are available free of charge at “https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.70928”, including experimental details, characterization data for all new compounds, ¹H‐, ¹³C‐, and 2D‐NMR spectra, and crystallographic data. Deposition numbers 2520695, 2520696, 2520699 contain the supplementary crystallographic data for this paper. This data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe. The raw NMR data are available upon request from the corresponding author or on nmrXiv at https://doi.org/10.57992/NMRXIV.P164.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Supporting Information: The authors have cited additional references within the Supporting Information [85, 86, 87, 88].

CHEM-32-e70928-s001.pdf^{(17.3MB, pdf)}

Data Availability Statement

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PERMALINK

A General Strategy for the Synthesis of Jerangolids Enabled by π‐allyl Stille Coupling

Janick Schug

Bernd Morgenstern

Johann Jauch

ABSTRACT

1. Introduction

FIGURE 1.

SCHEME 1.

2. Results and Discussion