The dual-catalyzed boryldifluoroallylation of alkynes: an efficient method for the synthesis of skipped gem-difluorodienes

Abstract

The Cu/Pd-catalyzed boryldifluoroallylation of alkynes was achieved, providing the skipped gem-difluorodiene scaffolds with high regio- and stereoselectivity. An array of synthetic building blocks can be obtained via further transformations.

Cu/Pd-Catalyzed cis-Borylfluoroallylation of Alkynes for the Synthesis of Boryl-Substituted Monofluoroalkenes

“…This proves that the diboron compound 13 is not an intermediate in the reaction. Integrating the results of the above mechanism experiments with those described in previous literature, , we propose the following mechanism (Scheme b). First, the Cu-catalyzed borylcupration of alkyne generates a borylalkenylcopper intermediate ( I ).…”

“…In 2020, Wang and coworkers described the trans-like, photoinduced fluorocarboborylation of alkynes with an integrated redox-active reagent (IMDN-SO 2 R F ) . Given these great achievements, the development of a three-component reaction that can introduce fluorine-containing fragments and boron groups into alkynes is very attractive.…”

Substrate-Controlled Cu(OAc)2-Catalyzed Stereoselective Semi-Reduction of Alkynes with MeOH as the Hydrogen Source

“…This may be attributed to the transmetalation process of the vinyl copper intermediate with B 2 pin 2 (see the Supporting Information ( SI ) for details). 15 …”

Recent Advances in the Construction of Fluorinated Organoboron Compounds

“…Moreover, in 2020, a dual-catalysis-promoted boryldifluoroallylation of alkynes was developed for the synthesis of boron-containing skipped gem -difluorodienes by Gong and Fu’s group 130 with high regio- and stereoselectivity ( Scheme 19 (ii)). This transformation goes through nucleophilic addition of alkynes, leading to alkenyl copper species A .…”