The construction of chiral 3-acyl bicyclolactams via a RuPHOX/Pd catalyzed asymmetric allylic substitution cascade of α-carbonylamides. Issue 7 (2nd March 2023)

• Record Type: Journal Article
• Authors: Dong, Siqi; Xu, Shaofeng; Zou, Yashi; Li, Zhaodi; Xu, Kai; Fu, Daxu; Liu, Delong; Zhang, Wanbin
• Is Part Of: Organic chemistry frontiers. Volume 10:Issue 7(2023)
• Page Start: 1731
• Page End: 1737
• Publication Date: 2023-03-02
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/d3qo00055a
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : A RuPHOX/Pd catalyzed asymmetric allylic substitution cascade of α-carbonylamides with an allylic meso -dicarbonate has been developed, providing chiral 3-acyl bicyclolactams in high yields and with up to 99% ee and >20 : 1 dr. Abstract : A RuPHOX/Pd catalyzed asymmetric allylic substitution cascade of α-carbonylamides with an allylic meso -dicarbonate has been developed, providing chiral 3-acyl bicyclolactams bearing three vicinal carbon stereocenters in high yields and with up to 99% ee and >20 : 1 dr. Mechanistic studies based on control experiments and DFT calculations revealed that a dynamic kinetic resolution process should occur during the second step of the cascade reaction, which is responsible for the excellent diastereoselectivities of the desired products. The protocol could proceed on a gram-scale and the resulting products allow for various transformations, especially for the preparation of several natural products.