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Published on: June 21, 2017
Stereoselective Radical C-H Alkylation with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based
Xin Cui1, Xue Xu1, Li-Mei Jin1
1Department of Chemistry, University of South Florida Tampa, FL 33620-5250 (USA)., ;
Abstract:
Co(II)-based metalloradical catalysis has been, for the first time, successfully applied for asymmetric intramolecular C-H alkylation of acceptor/acceptor-substituted diazo reagents. Through the design and synthesis of a new D2-symmetric chiral amidoporphyrin as the supporting ligand, the Co(II)-based metalloradical system, which operates at room temperature, is capable of 1,5-C-H alkylation of α-methoxycarbonyl-α-diazosulfones with a broad range of electronic properties, providing the 5-membered sulfolane derivatives in high yields with excellent diastereoselectivity and enantioselectivity. In addition to complete chemoselectivity toward allylic and allenic C-H bonds, the Co(II)-based metalloradical catalysis for asymmetric C-H alkylation features a remarkable degree of functional group tolerance.
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