Visible-light-induced decarboxylation/defluorosilylation protocol for synthesis ofgem-difluoroalkenes

Abstract

A catalytic defluorosilylation is disclosed that provides concise, modular synthetic entries to gem-difluoroallylsilanes from -trifluoromethylalkenes and silacarboxylic acids which are easy-to-prepare and stable silyl radical precursors. It is enabled by...

Decarboxylative Allylation of Silanecarboxylic Acids Enabled by Organophotocatalysis

“…The light “on–off” experiments ruled out radical chain pathways during the reaction process (Scheme b). Based on the above results and previous reports, − a presumable mechanism was illustrated (Scheme c). A single electron transfer (SET) between silanecarboxylate and excited 4CzIPN released carboxyl radical intermediate A along with the generation of 4CzIPN radical anion.…”

“…In addition, as analogues of carboxylic acids, silanecarboxylic acids can readily undergo decarboxylation to produce silyl radicals under mild and concise conditions. Recently, photocatalyzed decarboxylative alkylation, difluoroallylation, and heterocyclic arylation of silanecarboxylic acids were developed. On the other hand, as easily available allylating reagents, allyl sulfone derivatives have been extensively utilized for catalytic allylation reactions.…”

Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis

“…Moreover, their chemical properties are analogous to those of carboxylic acids, where radical decarboxylation readily occurs under mild and concise conditions. Heretofore, decarboxylative fictionalizations of silanecarboxylic acids have been scarcely studied, and only several examples, such as alkylation, allylation, difluoroallylation, and heterocyclic arylation, were documented. Intrigued by this, we report a regioselective hydrosilylation of 1,3-enynes with silanecarboxylic acids as the silylating sources.…”