Computational study of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes with CO2: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions. Issue 8 (18th March 2022)

• Record Type: Journal Article
• Authors: Hu, Yanlei; Hu, Lingfei; Gao, Han; Lv, Xiangying; Wu, Yan-Bo; Lu, Gang
• Is Part Of: Organic chemistry frontiers. Volume 9:Issue 8(2022)
• Page Start: 2240
• Page End: 2248
• Publication Date: 2022-03-18
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/d2qo00236a
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : The detailed mechanism of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes and origin of Cu-boryl additions have been investigated. Abstract : The mechanism and origin of regioselectivity of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes with CO2 were computationally investigated. The results show that CO2 not only acts as a carboxylation reagent, but also plays a critical role in the process of generating the key allyl copper intermediate, which is the active species for 1, 3-diene carboxylation with CO2 . The energy decomposition analysis indicates that Pauli repulsion is the dominant factor for controlling the regioselectivity of Cu–Bpin additions with 1, 3-dienes.