Combined Dynamic Kinetic Resolution and C−H Functionalization for Facile Synthesis of Non‐Biaryl‐Atropisomer‐Type Axially Chiral Organosilanes.

Li, Zhao; Wang, Xu; Cui, Yu‐Ming; Ma, Jun‐Han; Fang, Li‐Lei; Han, Lu‐Lu; Yang, Qin; Xu, Zheng; Xu, Li‐Wen

Although asymmetric C−H functionalization has been available for the synthesis of structurally diverse molecules, catalytic dynamic kinetic resolution (DKR) approaches to change racemic stereogenic axes remain synthetic challenges in this field. Here, a concise palladium‐catalyzed DKR was combined with C−H functionalization involving olefination and alkynylation for the highly efficient synthesis of non‐biaryl‐atropisomer‐type (NBA) axially chiral oragnosilanes. The chemistry proceeded through two different and distinct DKR: first, an atroposelective C−H olefination or alkynylation produced axially chiral vinylsilanes or alkynylsilanes as a new family of non‐biaryl atropisomers (NBA), and second, the extension of this DKR strategy to twofold o,o′‐C−H functionalization led to the multifunctional axially chiral organosilicon compounds with up to >99 % ee.

KINETIC resolution; ORGANOSILICON compounds; SILICON compounds; ATROPISOMERS; VINYLSILANES

Chemistry - A European Journal, 2021, Vol 27, Issue 13, p4336

0947-6539

Academic Journal

10.1002/chem.202100237