Enantioselective N-Allylic Alkylation of N-Propargylsulfonamides with Morita­–Baylis–Hillman Carbonates and Sequential Electrophilic Cyclization

Abstract

The enantioselective N-allylic alkylation of N-propargylsulfonamides with racemic Morita–Baylis–Hillman (MBH) carbonates catalyzed by modified cinchona alkaloids has been investigated. The alkylation products from MBH carbonates with a 4-methoxyphenyl group underwent ipso-iodocyclization to give optically active azaspirocyclohexadienones via electrophilic activation of alkyne group with iodine monochloride. In contrast, ortho-selective intramolecular Friedel–Crafts reaction occurred for intermediates from MBH carbonates with other electron-rich or neutral aryl or heteroaryl substitutions via the same activation strategy, delivering multifunctional 2-benzazepine frameworks in a highly enantioenriched­ form.

Key words

Morita–Baylis–Hillman carbonates - asymmetric allylic alkylation - electrophilic cyclization - azaspirocyclohexadienones - 2-benzazepines

• References


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