Enantioselective Radical SN2-Type Alkylation of Morita-Baylis-Hillman Adducts Using Dual Photoredox/Palladium Catalysis

Xiangbin Bai; Linlin Qian; Hong-Hao Zhang; Shouyun Yu

doi:10.1021/acs.orglett.1c03064

Enantioselective Radical S_N2-Type Alkylation of Morita-Baylis-Hillman Adducts Using Dual Photoredox/Palladium Catalysis

Org Lett. 2021 Nov 5;23(21):8322-8326. doi: 10.1021/acs.orglett.1c03064. Epub 2021 Oct 21.

Authors

Xiangbin Bai¹, Linlin Qian¹, Hong-Hao Zhang¹, Shouyun Yu¹

Affiliation

¹ State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.

PMID: 34672603
DOI: 10.1021/acs.orglett.1c03064

Abstract

An enantioselective radical alkylation of 4-alkyl-1,4-dihydropyridines with Morita-Baylis-Hillman (MBH) adducts has been reported. The S_N2-type products are predominant. This reaction is enabled by dual photoredox/palladium catalysis. The alkylation products are provided in good yields with good regio- and enantioselectivity. The use of Ding's spiroketal-based bis(phosphine) (SKP) ligand is crucial to achieving satisfactory regio- and enantioselectivity. The resultant α,β-unsaturated ester can be easily reduced to a synthetically useful chiral allyl alcohol.