Copper‐Catalyzed Highly Enantioselective Ring‐Opening/Cyclopropanation of 1‐Silylcyclopropenes DOI
Xianfei Wen, Zhan Wang, Jia‐Bao Zhao

и другие.

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

Comprehensive Summary The chiral cyclopropane framework is a crucial structural motif in bioactive molecules such as pharmaceuticals and natural products. Asymmetric cyclopropanation of alkenes via transition metal‐catalyzed carbene transfer represents one the most direct approaches for synthesizing cyclopropanes. While significant progress has been made asymmetric α‐C‐substituted carbenes, highly enantioselective α‐silyl which possess greater transformation potential, remains largely unexplored. In this study, we report Cu(I)/chiral bisoxazoline catalytic system that enables cyclopropanation/Cope rearrangement reactions between α‐silyl‐α‐alkenyl carbenes (generated from ring opening 1‐silyl cyclopropene) alkenes. This methodology provides access to series cyclopropylsilanes containing stereogenic quaternary carbon centers well allylic silane moieties cycloheptadienylsilanes, thereby expanding diversity organosilicon compounds. Theoretical calculations reveal rate‐determining step involves cyclopropene, where silyl group not only dictates regioselectivity but also significantly influences stereoselectivity reaction through its steric rigid properties.

Язык: Английский

Copper‐Catalyzed Highly Enantioselective Ring‐Opening/Cyclopropanation of 1‐Silylcyclopropenes DOI
Xianfei Wen, Zhan Wang, Jia‐Bao Zhao

и другие.

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

Comprehensive Summary The chiral cyclopropane framework is a crucial structural motif in bioactive molecules such as pharmaceuticals and natural products. Asymmetric cyclopropanation of alkenes via transition metal‐catalyzed carbene transfer represents one the most direct approaches for synthesizing cyclopropanes. While significant progress has been made asymmetric α‐C‐substituted carbenes, highly enantioselective α‐silyl which possess greater transformation potential, remains largely unexplored. In this study, we report Cu(I)/chiral bisoxazoline catalytic system that enables cyclopropanation/Cope rearrangement reactions between α‐silyl‐α‐alkenyl carbenes (generated from ring opening 1‐silyl cyclopropene) alkenes. This methodology provides access to series cyclopropylsilanes containing stereogenic quaternary carbon centers well allylic silane moieties cycloheptadienylsilanes, thereby expanding diversity organosilicon compounds. Theoretical calculations reveal rate‐determining step involves cyclopropene, where silyl group not only dictates regioselectivity but also significantly influences stereoselectivity reaction through its steric rigid properties.

Язык: Английский

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