Rhodium(I)-Catalyzed Asymmetric Alkyl Carbene B-H Bond Insertion: Enantioselective Synthesis of Versatile Chiral Alkylboranes

Open AccessCCS ChemistryRESEARCH ARTICLES19 Aug 2024Rhodium(I)-Catalyzed Asymmetric Alkyl Carbene B-H Bond Insertion: Enantioselective Synthesis of Versatile Chiral Alkylboranes Jian-Guo Liu, Bo Liu, Ziyan Li and Ming-Hua Xu Jian-Guo Liu , Bo Liu , Ziyan Li and Ming-Hua Xu Cite this: CCS Chemistry. 2024;0:1–26https://doi.org/10.31635/ccschem.024.202404591 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Recent advances have demonstrated that transition metal catalyzed asymmetric carbene B-H insertion reaction is a straightforward and powerful protocol to access chiral organoboron compounds, but the related reaction involving linear alkyl carbenes has not been successfully developed. Apart from the difficulty of controlling the enantioselectivity, another major challenge is the high propensity of the alkyl metal carbene to undergo a β-hydride migration to form undesired alkenes. Herein, we report our development of an efficient alkyl carbene B-H insertion reaction using rhodium(I)/diene complexes as the catalysts. This simple catalytic system can not only reduce the formation of alkene byproduct but also achieve highly enantioselectivity of carbene B-H insertion. The method facilitates facile asymmetric access to a wide variety of structurally diverse alkylboranes in high yields, and their further synthetic application and transformation have also been described. Mechanistic studies show that the β-hydride migration is less favorable than the carbene insertion pathway under rhodium(I)/diene catalytic system and the B-H bond insertion is the rate-limiting step. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2024 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...