Herein, we report an efficient method for the tertiary alkylation of a ketone by using an α‐bromocarbonyl compound as the tertiary alkyl source in a combined Cu‐organocatalyst system. This dual catalyst system enables the addition of a tertiary alkyl radical to an enamine. Mechanistic studies revealed that the catalytically generated enamine is a key intermediate in the catalytic cycle. The developed method can be used to synthesize substituted 1,4‐dicarbonyl compounds containing quaternary carbons bearing various alkyl chains.
Herein, we report a remote nucleophilic substitution
reaction via
1,4-hydrogen atom transfer (1,4-HAT) to synthesize N-acyl-N,O-acetal moieties. α-Bromocarboxamide
undergoes rSN at a C(sp3)–H bond in the
presence of an alcohol/phenol and a copper catalyst. Mechanistic studies
using deuterated α-bromocarboxamide confirmed that the 1,4-HAT
process is the rate-determining step. Topologically complex N-acyl-N,O-acetal molecules
can be accessed using our rSN reaction with various α-bromocarboxamides
via chemoselective reactions.
Herein, we report an efficient method for the tertiary alkylation of a ketone by using an α‐bromocarbonyl compound as the tertiary alkyl source in a combined Cu‐organocatalyst system. This dual catalyst system enables the addition of a tertiary alkyl radical to an enamine. Mechanistic studies revealed that the catalytically generated enamine is a key intermediate in the catalytic cycle. The developed method can be used to synthesize substituted 1,4‐dicarbonyl compounds containing quaternary carbons bearing various alkyl chains.
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