Organic chemistry

Ring (chemistry)

Stereochemistry

Dehydrogenation

Catalysis

Medicinal chemistry

Chemistry

Enamine

Hydrosilylation

Alkyl

Aryl

Intramolecular force

Piperidine

Silylation

Journal of the American Chemical Society

Described herein is the development of an unprecedented route to bridged sila-N-heterocycles via B(C6F5)3-catalyzed cascade silylation of N-aryl piperidines with hydrosilanes. Mechanistic studies indicated that an outer-sphere ionic path is operative to involve three sequential catalytic steps having N-silyl piperidinium borohydride as a resting species: (i) dehydrogenation of the piperidine ring, (ii) β-selective hydrosilylation of a resultant enamine intermediate, and (iii) intramolecular dehydrogenative sp2 C–H silylation.

Catalytic Access to Bridged Sila-N-heterocycles from Piperidines via Cascade sp3 and sp2 C–Si Bond Formation