Iridium‐Catalyzed Enantioselective C(sp3)−H Borylation of Aminocyclopropanes. (14th March 2022)

• Record Type: Journal Article
• Authors: Shi, Yongjia; Yang, Yuhuan; Xu, Senmiao
• Is Part Of: Angewandte Chemie. Volume 134:Number 19(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-14
• Subjects: Aminocyclopropanes -- Asymmetric Catalysis -- Bidentate Boryl Ligands -- C−H Borylation -- Iridium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202201463
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Transition‐metal‐catalyzed regio‐ and stereo‐controllable C−H functionalization remains a formidable challenge in asymmetric catalysis. Herein, we disclose the first example of iridium‐catalyzed C(sp 3 )−H borylation of aminocyclopropanes by using simple imides as weakly coordinating directing groups under mild reaction conditions. The reaction proceeded via a six‐membered iridacycle, affording a vast range of chiral aminocyclopropyl boronates. The current method features a broad spectrum of functional groups (36 examples) and high enantioselectivities (up to 99 %). We also demonstrated the synthetic utility by a preparative scale C−H borylation, C−B bond transformations, and conversion of the directing group. Abstract : The first example of simple imide‐directed intermolecular enantioselective C(sp 3 )−H functionalization of aminocyclopropanes enabled by iridium catalysis has been developed. The reaction proceeds via six‐membered metallacycles. The method could tolerate a broad spectrum of functional groups, affording a vast array of chiral aminocyclopropanes (36 examples) with high enantioselectivities (up to 99 % ee ).