Subscribe to RSS
DOI: 10.1055/a-2338-4544
Enantioselective α-Boryl Carbene Transformations
We thank the National Key R&D Program of China (2021YFA1500200), National Natural Science Foundation of China (22301145, 92256301, 92156006, 22221002), the ‘111’ project (B06005) of the Ministry of Education of China, Haihe Laboratory of Sustainable Chemical Transformations, the Fundamental Research Funds for the Central Universities, Natural Science Foundation of Tianjin (63231033) and New Corner-stone Science Foundation through the XPLORER PRIZE for financial support.
Abstract
α-Boryl carbenes, which are hybrid structures combining elements of carbenes and boryl groups, represent promising intermediates for constructing organoboron compounds. However, these carbenes are challenging to synthesize and exhibit limited structural diversity. Moreover, their applications in asymmetric transformations remain largely unexplored. In this study, we utilized boryl cyclopropenes as precursors to rapidly synthesize α-Bpin metal carbenes, a novel category of intermediates critical for the synthesis of chiral organoboron molecules. Facilitated by a copper complex modified by a chiral bisoxazoline ligand, these α-boryl carbenes participate in a range of highly enantioselective transfer reactions, including B–H and Si–H insertions, as well as cyclopropanation and cyclopropanation/Cope rearrangement processes. This methodology provides access to previously inaccessible, yet highly useful, chiral organoborons, thereby significantly advancing both carbene and organoboron chemistry.
1 Introduction
2 Previous Discovery and Our Design
3 Copper Catalyzed Enantioselective α-Boryl Carbene Transfer Reactions
4 Mechanistic Studies
5 Conclusions
Key words
α-boryl carbenes - asymmetric catalysis - cyclopropenes - carbene transfer reactions - chiral organoboronsPublication History
Received: 18 April 2024
Accepted after revision: 04 June 2024
Accepted Manuscript online:
04 June 2024
Article published online:
25 June 2024
© 2024. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Wang J.-B, Che C.-M, Doyle MP. Transition Metal-Catalyzed Carbene Transformations . Wiley-VCH; Weinheim: 2022
- 2a Jia M.-Q, Ma S.-M. Angew. Chem. Int. Ed. 2016; 55: 9134
- 2b Huang M.-Y, Zhu S.-F. Chem Catal. 2022; 2: 3112
- 3 Zhang L.-M, DeMuynck BM, Paneque AN, Rutherford JE, Nagib GA. Science 2022; 377: 649
- 4 Marinozzi M, Pertusati F, Serpi M. Chem. Rev. 2016; 116: 13991
- 5 Zhu S.-F, Ruppel JV, Lu H.-J, Wojtas L, Zhang XP. J. Am. Chem. Soc. 2008; 130: 5042
- 6 Caló FP, Fürstner A. Angew. Chem. Int. Ed. 2020; 59: 13900
- 7 Hooz J, Gunn DM. J. Am. Chem. Soc. 1969; 91: 6195
- 8a Schollkopf U, Banhidai B, Frasnelli H, Meyer R, Beckhaus H. Justus Liebigs Ann. Chem. 1974; 1767
- 8b Arthur MP, Baceiredo A, Bertrand G. J. Am. Chem. Soc. 1991; 113: 5856
- 8c Weber L, Wartig HB, Stammler H.-G, Neumann B. Organometallics 2001; 20: 5248
- 8d Sotiropoulos JM, Baceiredo A, Vonlocquenghien KH, Dahan F, Bertrand G. Angew. Chem., Int. Ed. Engl. 1991; 30: 1154
- 8e Ansorge A, Brauer DJ, Burger H, Hagen T, Pawelke G. Angew. Chem., Int. Ed. Engl. 1993; 32: 384
- 9 Liu Y, de la Bellacasa RP, Li B, Cuenca AB, Liu S. J. Am. Chem. Soc. 2021; 143: 14059
- 10 Li S.-C, Li M.-Y, Li S.-S, Wang J.-B. Chem. Commun. 2022; 58: 399
- 11 Zheng Y, Jiang J.-X, Li Y, Wei Y.-L, Zhang J.-Q, Hu J.-D, Ke Z.-F, Xu X.-F, Zhang L.-M. Angew. Chem. Int. Ed. 2023; 62: e202218175
- 12a Zhu S.-F, Zhou Q.-L. Acc. Chem. Res. 2012; 45: 1365
- 12b Huang M.-Y, Zhu S.-F. Chem. Sci. 2021; 12: 15790
- 12c Zhu S.-F. Chin. J. Chem. 2021; 39: 3211
- 12d He Y.-M, Cheng Y.-Z, Duan Y, Zhang Y.-D, Fan Q.-H, You S.-L, Luo S.-Z, Zhu S.-F, Fu X.-F, Zhou Q.-L. CCS Chem. 2023; 5: 2685 For recent examples, see
- 12e Guo F.-K, Lu Y.-L, Huang M.-Y, Yang J.-M, Guo J.-LWan Z.-Y, Zhu S.-F. Sci. Adv. 2023; 9: eadj2486
- 12f Zou H.-N, Huang M.-L, Huang M.-Y, Su Y.-X, Zhang J.-W, Zhang X.-Y, Zhu S.-F. Chem. Sci. 2023; 14: 9186
- 12g Zou H.-N, Zhao Y.-T, Yang L.-L, Huang M.-Y, Zhang J.-W, Huang M.-L, Zhu S.-F. ACS Catal. 2022; 12: 10654
- 12h Zhao Y.-T, Su Y.-X, Li X.-Y, Yang L.-L, Huang M.-Y, Zhu S.-F. Angew. Chem. Int. Ed. 2021; 60: 24214
- 13a Huang M.-Y, Zhao Y.-T, Zhang C.-D, Zhu S.-F. Angew. Chem. Int. Ed. 2022; 61: e202203343
- 13b Huang M.-Y, Zhao Y.-T, Chai H, Zhang C.-D, Zhu S.-F. CCS Chem. 2022; 4: 1232
- 14 Huang M.-Y, Zhao J.-B, Zhang C.-D, Zhou Y.-J, Lu Z.-S, Zhu S.-F. J. Am. Chem. Soc. 2024; 146: 9871
- 15 Falivene L, Cao Z, Petta A, Serra L, Poater A, Oliva R, Scarano V, Cavallo L. Nat. Chem. 2019; 11: 872
- 16 Dapprich S, Frenking G. J. Phys. Chem. 1995; 99: 9352
- 17 Parr RG, Szentpály LV, Liu S. J. Am. Chem. Soc. 1999; 121: 1922
For selected examples of α-boryl diazo compounds, see:
For reviews, see: