☆ 4.8 Article

Enantioselective Synthesis of Dihydropyridines Containing Quaternary Stereocenters Through Dearomatization of Pyridinium Salts

ACS CATALYSIS (2020)

期刊

ACS CATALYSIS

卷 10, 期 1, 页码 51-55

出版社

AMER CHEMICAL SOC

DOI: 10.1021/acscatal.9b03874

关键词

heteroarene dearomatization; asymmetric catalysis; heterocycles; rhodium catalysis; dihydropyridines

类别

Chemistry, Physical

资金

Auburn University

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摘要

Enantioselective synthesis of nonaromatic heterocycles containing a fully substituted stereogenic center is a challenging synthetic problem. We describe a strategy toward this problem involving dearomatization of N-alkylpyridinium salts using boronic acid nucleophiles. This dearomatization reaction is catalyzed by a rhodium(I)/BINAP catalytic system and delivers dihydropyridines that contain a fully substituted stereogenic center alpha to the ring nitrogen atom in high yields and enantioselectivities. The reaction is compatible with a wide range of functional groups such as halide, ester, amide, olefin, and free alcohol. Derivatization of dehydropyridine products allows synthesis of the functionalized tetrahydropyridines and piperidines.

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