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. 2024 Jul 24;10(30):eadn8401. doi: 10.1126/sciadv.adn8401

N-Heterocyclic carbene catalytic 1,2-boron migrative acylation accelerated by photocatalysis

Hua Huang 1,2, Zhao-Yuan Yu 2, Lu-Yao Han 1,2, Yi-Qi Wu 2, Lu Jiang 2, Qing-Zhu Li 2, Wei Huang 1, Bo Han 1,*, Jun-Long Li 1,2,*
PMCID: PMC11268412  PMID: 39047096

Abstract

The transformation of organoboron compounds plays an important role in synthetic chemistry, and recent advancements in boron-migration reactions have garnered considerable attention. Here, we report an unprecedented 1,2-boron migrative acylation upon photocatalysis-facilitated N-heterocyclic carbene catalysis. The design of a redox-active boronic ester substrate, serving as an excellent β-boron radical precursor, is the linchpin to the success of this chemistry. With the established protocol, a wide spectrum of β-boryl ketones has been rapidly synthesized, which could further undergo various C─B bond transformations to give multifunctionalized products. The robustness of this catalytic strategy is underscored by its successful application in late-stage modification of drug-derived molecules and natural products. Preliminary mechanistic investigations, including several control experiments, photochemistry measurements, and computational studies, shed light on the catalytic radical reaction mechanism.

An unprecedented NHC catalytic 1,2-boron migrative acylation accelerated by photocatalysis is reported.

INTRODUCTION

Organoboron compounds play a pivotal role in diverse fields of physical science, encompassing chemistry (1, 2), materialogy (3), energy research (4), and pharmaceutical sciences (5). In particular, the integration of boron functional groups into natural products or bioactive compounds can bestow them with unique pharmacological properties, thereby facilitating the discovery of boron-containing drugs (6, 7). For instance, bortezomib, serving as a reversible and selective proteasome inhibitor, is used in treating multiple myeloma (8); numidargistat functions as an inhibitor of ARG1 (arginase 1) and is used to combat metastatic solid tumors (9); AN3365, a potent and selective leucyl-tRNA synthetase inhibitor, exhibits inhibitory activity against Gram-negative bacteria (Fig. 1A, I) (10). Consequently, the quest for efficient methodologies in creating organoboron compounds remains of paramount importance.

Fig. 1. Backgrounds of this study and research motivation.

Fig. 1.

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(A) The importance of boron-containing molecules. (B) Radical-induced 1,2-boryl migration. (C) Combining NHC catalysis with the atom migration strategy. (D) This work: NHC/PC-catalyzed 1,2-boron migrative acylation.

In addition, organoboranes exhibit unique and versatile reactivity, commonly serving as key intermediates for various high-value transformations. For example, the C─B bond can be readily converted into C─C and C─X bonds through reactions such as the Suzuki-Miyaura (11, 12) and Chan-Lam couplings (13), as well as other cross-coupling reactions (14). The C─B bond can also undergo oxidative hydrolysis (15) or protodeboronation (16) to access the corresponding alcohol and hydrocarbon compound. While those methods have indeed broadened the scope of boron chemistry, they primarily focus on diversifying the boron moiety, thereby constraining the functionalization of organoboron compounds to boron-discarded transformations. In contrast, the boron-retaining reactions have recently garnered substantial interest, because the resulting boron-containing products are not only valuable compounds in their own right but can also undergo additional C─B bond transformations, thus facilitating the creation of multifunctionalized products (Fig. 1A, II). In this evolving field, the strategy of boryl migration represents a convenient approach to obtain boron-retained products, with numerous elegant studies related to 1,2-boron migration (17–23).

While extensive research has been conducted on 1,2-migrations involving tetracoordinated borate species, investigations into radical-induced 1,2-boron migrations have remained relatively limited (24–26). In 1999, Batey and Smil (27) reported the first radical strategy for 1,2-boryl migration. In this reaction, the key intermediate, a β-boron radical species, was generated via intramolecular radical addition to alkenes, allowing for subsequent 1,2-boryl migration. Recently, Studer and co-workers achieved the intermolecular radical 1,3-difunctionalization by using simple allylboron as the boryl migrative substrates (28, 29). Aggarwal and colleagues developed an alternative approach to generate β-boron radicals through the photocatalytic single-electron oxidation of 1,2-diborate substrates (Fig. 1B, I) (30–32).

Nonetheless, radical-induced 1,2-boron migrations are reported infrequently, possibly due to the limited strategies available for β-boron radical generation. Besides the reported radical addition and single-electron oxidation strategies, we hypothesized that β-boron radical intermediates might also be generated through single-electron reduction by introducing an electron acceptor at the β-position of the boron functional group. On the basis of these considerations, we have designed and synthesized a boronic ester substrate bearing a redox-active functionality at β-position (Fig. 1B, II) (33). This building block can readily accept an electron from the reaction system and generate a β-boron radical species, offering potential avenues for the reaction developments involving 1,2-boryl migration.

Very recently, radical N-heterocyclic carbene (NHC) catalysis has seen notable advancements (34–55). In particular, the combination of radical NHC catalysis with hydrogen atom transfer (HAT) strategy has emerged as a powerful tool for the development of challenging chemical reactions (56–62). In this realm, Ohmiya, Chi, our group, and others have revealed that the functionalization of inert sp3 C─H bonds can be accomplished with HAT strategy in NHC catalytic systems (Fig. 1C, I). Nevertheless, aside from hydrogen atoms, there are currently no reports on the migration of other heteroatom groups mediated by NHC catalysis (Fig. 1C, II).

Building on our continued interest in this direction, we present an unprecedented radical-induced 1,2-boron migrative acylation approach utilizing the NHC and photoredox cooperative catalysis. The newly developed β-boryl ester substrates can successfully offer the β-boron radical intermediate through SET reduction. With this protocol, a wide spectrum of β-acyl boron compounds has been accessed in a straightforward manner, which could further undergo various C─B bond transformations to give multifunctionalized products. This approach is also suitable for late-stage modifications of pharmaceutical molecules and natural products. Preliminary mechanistic studies of the catalytic reaction were conducted through a series of mechanistic experiments and density functional theory (DFT) calculations (Fig. 1D).

RESULTS

Optimization of the reaction conditions

We started our investigation by selecting aldehyde 1a and β-boryl N-hydroxyphthalimide (NHPI) ester 2 as model substrates, in the presence of [Ir(ppy)2(dtbbpy)]PF6 as the photocatalyst under blue light-emitting diode (LED) irradiation. The N-2,6-diisopropylphenyl substituted cycloheptane-fused thiazolium N1 was selected as the NHC precatalyst in combination with Cs2CO3 as the base. As illustrated in Table 1, several solvents were first screened (entries 1 to 4), and we found that the desired 1,2-boron migrative acylation worked best in DCM, delivering product 3a in 34% isolated yield. Then, structural modification of NHPI esters was conducted, and diverse leaving groups on β-boryl esters were evaluated. As shown in entries 5 to 7, the tetrachloro-substituted NHPI (TCNHPI) ester was found to be the optimal substrate. Next, the investigation encompassed various photocatalysts, including the structurally diverse iridium-based photocatalysts and the acridine photocatalyst, whose yields remained similar or had a slight decrease (entries 8 to 11). Subsequently, we screened the pre-NHC organocatalysts, but other thiazolium-based NHCs N2-N3 led to inferior results (entries 12 and 13). The 1,2-boron migrative acylation reaction did not occur in the presence of either triazolium NHC precursor or mesoionic carbene (entries 14 and 15). Further screening of inorganic and organic bases did not improve the reaction outcome (entries 16 to 19). Last, we explored mixed-solvent systems by combining different kinds of solvents (63, 64), and we were delighted to find that the isolated yield of this reaction could be improved to 73% by using the 4:1 mixture of the DCM/THF solvent (entries 20–22).

Table 1. Optimization studies.

Reaction condition: 1a (0.10 mmol), 2 (0.15 mmol), base (0.10 mmol), PC (2% mmol), and NHC (0.02 mmol) in solvent (2.0 ml), irradiation with blue LEDs. THF, tetrahydrofuran; DCM, dichloromethane; DBU, 1,8-diazabicyclo [5.4.0] undec-7-ene.

graphic file with name sciadv.adn8401-t1.jpg

Entry NHC PC Ester Solvent Base Yield (%)* Entry NHC PC Ester Solvent Base Yield (%)*
1 N1 PC1 2a Toluene Cs2CO3 25 12 N2 PC1 2b DCM Cs2CO3 <5
2 N1 PC1 2a THF Cs2CO3 30 13 N3 PC1 2b DCM Cs2CO3 <5
3 N1 PC1 2a MeCN Cs2CO3 <5 14 N4 PC1 2b DCM Cs2CO3 <5
4 N1 PC1 2a DCM Cs2CO3 34 15 N5 PC1 2b DCM Cs2CO3 <5
5 N1 PC1 2b DCM Cs2CO3 60 16 N1 PC1 2b DCM K2CO3 42
6 N1 PC1 2c DCM Cs2CO3 45 17 N1 PC1 2b DCM CsHCO3 49
7 N1 PC1 2d DCM Cs2CO3 45 18 N1 PC1 2b DCM DBU 20
8 N1 PC2 2b DCM Cs2CO3 55 19 N1 PC1 2b DCM TEA <5
9 N1 PC3 2b DCM Cs2CO3 58 20† N1 PC1 2b DCM/THF Cs2CO3 50
10 N1 PC4 2b DCM Cs2CO3 52 21‡ N1 PC1 2b DCM/THF Cs2CO3 49
11 N1 PC5 2b DCM Cs2CO3 55 22§ N1 PC1 2b DCM/THF Cs2CO3 73
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*Isolated yield of 3a.

†DCM/THF = 1/1.

‡DCM/THF = 3/2.

§DCM/THF = 4/1.

Scope of the reaction

With the optimized conditions in hand, we set out to investigate the generality and limitation of the NHC-catalyzed 1,2-boron migrative acylation accelerated by photocatalysis. As shown in Fig. 2, the scope of aldehydes 1 was first examined. Various aromatic aldehydes bearing diverse para- or meta-substituents featuring either electron-withdrawing or electron-donating characteristics were well tolerated, offering the corresponding 1,2-boron migrated ketone products 3a–3i in 43%–75% yields. CCDC 2247103 (3a) contain the supplementary crystallographic data for this paper, and please see the Supplementary Materials for more details. The ortho-substituted aromatic aldehyde was also tolerated in the catalytic system, leading to the production of 3j in moderate yield. In addition, the bis-substituted aldehydes were suitable substrates for this reaction, affording products 3k to 3n in 45 to 63% yields. The naphthyl aldehyde was compatible in this reaction, delivering the corresponding product 3o in 72% yield. Moreover, reactions involving various heteroaryl aldehydes, such as thienyl, furyl, and pyridyl aldehydes, showed good performance in producing 3q to 3s. However, when the aliphatic aldehyde such as benzenepropanal and cyclopentanecarbaldehyde were tested, a decrease in reaction efficiency was observed (3t to 3u). Then, the scope of β-boryl TCNHPI esters was evaluated. As illustrated in the bottom half of Fig. 2, various electron-rich or electron-deficient substituents at the para- or meta-position on the aryl group of the TCNHPI substrates were well tolerated, offering 3v to 3z in 46 to 63% isolated yields. Notably, the ortho-substituted β-boryl TCNHPI esters could successfully afford the desired products 3aa to 3ac in 41, 60, and 65% yield, respectively. In addition, the non-benzylic TCNHPI esters were tolerated, affording products 3ad to 3an in 15 to 77% yield. Moreover, the α-substituted TCNHPI substrates could successfully afford the desired products 3ao to 3ap in 72 and 68% yield, respectively. Furthermore, we have examined different boron moieties for the radical 1,2-boron migration, such as B-hex (bis-hexylene glycolato diboron), B-nep (bis-neopentyl glycolato diboron), and B-oct (bis-2,4-dimethylpentane-2,4-glycolato diboron). To our gratification, these functionalities were all compatible with our NHC catalytic system to give the desired 1,2-boron shifted products 3aq to 3as in 70 to 84% yields.

Fig. 2. Substrate scope for the catalytic reactions of aldehyde 1 with 2.

Fig. 2.

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(A) Aldehyde scope. (B) β-boron TCNHPI ester. Reaction condition: 1 (0.10 mmol), 2 (0.15 mmol), Cs2CO3 (0.10 mmol), PC1 (2% mmol), and N1 (0.02 mmol) in 4:1 mixture of the DCM/THF solvent (2.0 ml), irradiation with blue LEDs. *DCM (0.05 M) as the solvent. †N2 as the NHC catalyst, K3PO4 as the base, PC5 as the photocatalyst, and toluene (0.1 M) as the solvent. ‡For detailed reaction condition, see the Supplementary Materials.

To further showcase the generality of this protocol, we applied the established catalytic system to the late-stage functionalization of pharmaceutical skeletons or natural products (65, 66), and the results are summarized in Fig. 3. Diflunisal, tolmetin, and naproxen are nonsteroidal anti-inflammatory drugs that are widely used in clinical practice to treat rheumatoid arthritis and osteoarthritis. We found that the aldehydes derived from diflunisal, tolmetin, and naproxen were suitable substrates in our reaction, leading to the production of drug-like molecules 4, 5, and 6 in 71, 70, and 53% yield, respectively. In addition, the dicamba- and isoxepac-derived aldehydes smoothly participated in the 1,2-boron migrative acylation, offering 7 and 8 in 55 to 58% yields. The aldehyde derivatives of ciprofibrate, a phenoxy acetic acid–based lipid-lowering drug, could also be tolerated in the catalytic acylation reaction, affording the corresponding boryl-ketone 9 in 32% yield. Moreover, the aldehydes derived from natural products, such as citronellol and pterostilbene, could work very efficiently with the TCNHPI ester 2b, delivering the 1,2-boron shifted ketone products 10 and 11. In addition, various TCNHPI esters were tested in the presence of zingerone-derived aldehydes, affording a series of drug-like molecules 12a to 12g in high efficiency.

Fig. 3. Late-stage functionalization by using the drug-derived or natural product-derived aldehydes.

Fig. 3.

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Reaction condition: 1 (0.10 mmol), 2 (0.15 mmol), Cs2CO3 (0.10 mmol), PC1 (2% mmol), and N1 (0.02 mmol) in a 4:1 mixture of the DCM/THF solvent (2.0 ml), irradiation with blue LEDs. *DCM (0.05 M) as the solvent.

Further exploration of synthetic applications

Next, several synthetic transformations were performed to demonstrate the practicality and versatility of this method. First, the 1,2-boron migrative acylation could be scaled up to 1 mmol scale by using either 4-bromobenzaldehyde 1a or benzaldehyde 1p, albeit with a slight decrease in yield (Fig. 4A). Then, the functional group diversification of the boron-retaining ketone 3p was investigated. As shown in Fig. 4B, the Suzuki–Miyaura cross-coupling reaction of 3p with 4-bromotoluene or 2-bromo-naphthalene gave the arylated products 13 and 14 in 89 and 81% isolated yield, respectively. Treatment of 3p with vinyl magnesium bromide and I2 afforded the vinylated product 15 in 78% yield. Then, we planned to prepare a protodeboronation product by using Aggwaral’s lithiation-borylation protocol (16); however, an unexpected α,β-unsaturated ketone 16 was isolated. Moreover, the β-boryl ketone could be easily oxidized to give the corresponding alcohol 17 in 80% yield. The Bpin group could also be transformed into the more stable trifluoroborate salt 18 in 76% yield. Next, the removal of ketone functionality by using triethyl silane delivered the aliphatic boron product 19 in 52% yield. To test the feasibility of an asymmetric variant of radical organocatalysis, a unique type of chiral thiazolium NHC catalyst N6, which was designed and synthesized by our group (67), was utilized in this reaction. With this chiral catalyst, the desired asymmetric 1,2-boron migrative acylation of 1a and 2b proceeded efficiently and afforded the enantioenriched product 3a in 50% yield with 74:26 enantioselective ratio (Fig. 4C) (for detailed screening of the asymmetric version, see the Supplementary Materials).

Fig. 4. Scale-up reaction, synthetic elaboration, and the attempt for an asymmetric version.

Fig. 4.

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(A) Scale-up experiments. (B) Synthetic applications of 3p. (C) Asymmetric catalysis. Reaction conditions: (I) Pd2(dba)3, Ruphos, NaOtBu, and toluene/H2O; (II) vinylmagnesium bromide, I2, THF, and MeOH; (III) TBAF·3H2O, Cu(OAc)2, TBC, and DCE; (IV) H2O2, NaOH, and THF; (V) KHF2 and MeOH; (VI) Et3SiH and TFA.

Mechanism studies

The mechanism of this photocatalysis-facilitated NHC-catalyzed radical reaction was investigated by performing several control experiments. As shown in Fig. 5, we found that the desired product was not generated without using an NHC catalyst. In the absence of PC1 and light irradiation at room temperature, neither NHPI ester 2a nor TCNHPI ester 2b yielded any product. However, while using 2a still did not yield any product, using substrate 2b resulted in the successful formation of the target product 3a in 40% yield at 50°C (Fig. 5A). Moreover, the ultraviolet (UV)–vis absorption spectrum of the photocatalyst [Ir(ppy)2(dtbbpy)]PF6 revealed a strong absorption of visible light. By contrast, no visible light absorption was observed for the substrates, NHC catalysts, or their combinations (Fig. 5B). These results indicated that the photocatalytic process was initiated by the excitation of photocatalyst. Besides, we also performed Stern-Volmer luminescence quenching experiments. As illustrated in Fig. 5C, the excited state of PC1 could be readily quenched by β-boryl TCNHPI ester, rather than the aldehyde 1a, NHC catalyst, base, or their combinations. Next, the results of the light on-off experiment and measurement of the quantum yield suggest that the reaction followed a catalytic radical process, rather than a radical chain pathway (for details, see the Supplementary Materials). Furthermore, the reduction potential of β-boryl TCNHPI ester 2b (Ered = −0.91 V versus SCE) was measured by cyclic voltammetry analysis. Compared with the oxidation potential of the excited [Ir(ppy)2(dtbbpy)]PF6 (E1/2* III/IV = −0.96 V versus SCE), a single-electron transfer between the excited photocatalyst and β-boryl TCNHPI ester 2b is feasible.

Fig. 5. Experimental mechanistic investigations.

Fig. 5.

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(A) Control experiments. (B) UV-vis absorption. (C) Luminescence quenching experiments. a.u., arbitrary units. *At room temperature. †At 50°C.

To gain further insights into the mechanism of this NHC-catalyzed 1,2-boron migrative acylation, we examined the competing pathways, which would stem from the diverse transformations of the radical intermediate IM-1, by using DFT calculations (for detailed data, see the Supplementary Materials). As shown in Fig. 6A, starting from IM-1, the transition state TS1–3 corresponds to a direct radical coupling process with a free energy barrier of 9.7 kcal/mol. In contrast, the 1,2-boron migration that leads to the formation of radical intermediate IM-4 proceeds through the transition state TS1–4, with a lower energy barrier of 7.5 kcal/mol. Moreover, the radical intermediate IM-4 is more stable than the intermediate IM-1 by 12.9 kcal/mol, which is quite reasonable because the stability of general, simple alkyl radicals follows the following trend: secondary > primary. This computational result reveals that the 1,2-boron migration pathway that gives radical intermediate IM-4 is kinetically more favorable than the direct radical coupling pathway (IM-1 → IM-3). Next, the radical cross-coupling involving intermediate IM-4 via transition state TS4–5 gives the adduct IM-5, overcoming a Gibbs energy barrier of 10.5 kcal/mol. Last, the release of NHC catalyst IM-6 affords the target acylated product 3 via TS5–6. Meanwhile, we also considered and calculated an alternative radical coupling pathway, in which radical IM-1 and IM-4 first coupled at the thiazolylidene moiety of the oxidized Breslow intermediate IM-2 followed by 1,2-carbon migration (68) (for detailed calculation of this pathway, see the Supplementary Materials).

Fig. 6. DFT studies and proposed mechanism of the 1,2-boron migrative acylation.

Fig. 6.

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(A) Energy profiles calculated for the NHC-catalyzed radical coupling processes from IM-1 and IM-4. (B) Proposed reaction mechanism.

On the basis of the above experimental and computational results, the mechanism of this reaction is suggested in Fig. 6B. One possible reaction pathway is that the photocatalyst Ir(III) was excited upon irradiation of visible light. Then, single-electron transfer from the excited PC Ir(III)* to the TCNHPI ester 2 generated an alkyl radical IV and the corresponding oxidized PC Ir(IV). Next, the alkyl radical IV would transform into a more stable radical V through a facile 1,2-boron migration. In parallel, aldehyde 1 condensed with the carbene catalyst I to form the deprotonated Breslow intermediate II under alkaline conditions. Subsequently, the electron-rich Breslow intermediate underwent a single-electron transfer with the PC Ir(IV), resulting in the regeneration of the ground state of PC Ir(III) and a Breslow intermediate-derived ketyl radical species III. An alternative pathway is that heating conditions can promote a direct single-electron transfer between Breslow intermediate II and TCNHPI ester 2, generating an alkyl radical IV, which would then transform into a more stable radical V and a ketyl radical species III. Consequently, the radical-radical cross-coupling between the persistent ketyl radical (69) and the radical V occurred. Last, the NHC catalyst was released to close the catalytic cycle and afforded the product 3.

DISCUSSION

In summary, we have developed an unprecedented NHC catalytic 1,2-boron migrative acylation accelerated by photocatalysis. The key to the success of this reaction lies in the design of a unique TCNHPI boronic ester substrate, which could serve as β-boron radical precursors through a single-electron reduction event. With this catalytic protocol, a broad spectrum of β-boryl ketones could be rapidly accessed under mild conditions, which could further undergo various C─B bond diversifications to offer multifunctionalized ketone products. The generality of this method is demonstrated through late-stage modifications of pharmaceutical molecules and natural product derivatives. In addition, we have explored the feasibility of asymmetric catalysis for this transformation, although only moderate enantioselectivity was achieved using our chiral NHC catalyst at the current stage. Preliminary mechanistic investigations, including a series of control reactions, photochemistry experiments, and DFT calculations, have been undertaken to provide insight into the NHC catalytic acylation with concomitant 1,2-boron migration. Our ongoing research in the application of NHC radical catalysis to various functional group migrations will be reported in due course.

MATERIALS AND METHODS

General procedures

Unless stated otherwise, all reactions were carried out under an atmosphere of Ar. Commercial reagents and solvents were obtained from Adamas-beta, Aldrich Chemical Co., Alfa Aesar, Macklin, Energy Chemical, and Leyan. Ir(ppy)2(dtbbpy)(PF6) (70) and triazolium salt N1 (71) were synthesized according to the literature procedures. Analytical thin-layer chromatography was performed on silica gel HSGF254 glass plates (purchased from Jiangyou Silica Gel Development Co. Ltd., Yantai, China) containing a 254-nm fluorescent indicator. Flash column chromatography was performed over silica gel (40 to 45 μm, 300 to 400 mesh). 1H nuclear magnetic resonance (NMR), 13C NMR, 11B NMR, and 19F NMR spectra were recorded at 25°C on a JEOL JNM-ECZ600R/S1 spectrometer. High-resolution mass spectra were performed on an Agilent 6230 time-of-flight liquid chromatography-mass spectrometry instrument or a Waters SYNAPT G2 mass spectrometer by using an electrospray ionization source analyzed by quadrupole time of flight. Melting points were determined on an SGW X-4 digital melting point apparatus and temperatures were not corrected. UltraPerformance Convergence Chromatography (UPCC) was performed on a Waters Acquity UPCC, using a chiralpak OD3 column eluted with carbon dioxide and isopropyl alcohol.

General procedure for the NHC/PC dual catalytic 1,2-boron migrative acylation

The β-boryl TCNHPI esters 2 (0.15 mmol, 1.5 equiv), N1 (0.20 mmol, 0.2 equiv), and PC1 (2% mmol) were added to a dried Schlenk tube. The tube was then evacuated and back-filled with argon three times. Under Ar protection, aldehydes 1 (0.10 mmol, 1.0 equiv), Cs2CO3 (0.10 mmol, 1.0 equiv), and a 4:1 mixture of the DCM/THF solvent (2.0 ml) were subsequently added. The resulting mixture was stirred for 1.0 to 3.0 hours under blue LED irradiation. Afterward, the reaction mixture was concentrated under reduced pressure. The resulting crude material was purified through column chromatography on silica gel with petroleum ether and ethyl acetate (60:1, 50:1, to 30:1) as eluents to afford the products 3.

Acknowledgments

Funding: Financial support from the NSFC (22271028, 22203010, 82374020, and 22071011), the Science and Technology Department of Sichuan Province (2023NSFSC2001), the Longquan Talents Program, Key-Area Research and Development Program of Guangdong Province (2022B1111050003), and the Research Funding from Chengdu University is acknowledged.

Author contributions: J-L.L. designed the project. H.H. conducted the main experiments and prepared the Supplementary Materials. Z.-Y.Y. performed the DFT calculations. L.-Y.H. and Y.-Q.W. prepared some substrates and performed the mechanistic experiments. L.J. helped with characterizing some compounds. H.H., B.H., and J-L.L. wrote the manuscript. Q.-Z.L. and W.H. helped revise the manuscript. B.H. and J.-L.L. supervised the whole study.

Competing interests: The authors declare that they have no competing interests.

Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: compound 3a (CCDC 2247103).

Supplementary Materials

This PDF file includes:

Supplementary Text

Figs. S1 to S17

Tables S1 to S8

References

sciadv.adn8401_sm.pdf (19MB, pdf)

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Supplementary Materials

Supplementary Text

Figs. S1 to S17

Tables S1 to S8

References

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