Ligand-free copper-catalyzed borylative defluorination: access to gem-difluoroallyl boronic acid derivatives

Abstract

We report a ligand-free copper-catalyzed α-borylation, defluorination of β-substituted, α-trifluoromethyl-α,β-unsaturated esters. The reaction affords geminal-difluoroallyl boronic acid derivatives in moderate to good yield. The reaction was tolerant of various substrates...

Enantioselective Copper-Catalyzed sp2/sp3 Diborylation of 1-Chloro-1-Trifluoromethylalkenes

“…Fluorine-containing organoboron compounds have emerged as novel synthons in chemical synthesis due to the existence of two important functionalitiesfluorine and boron on one molecule scaffold, which brings versatility and complexity to the eventual products. − Among them, the fluorinated ones bearing multiple types of C–B bonds are particularly appealing, since they might undergo chemoselective and diversified transformations on different C–B bonds, leading to well-controlled and multifunctionalized complex targeted molecules . However, successful examples of constructions of multiborylated compounds with distinct C–B bonds are very rare, particularly for enantioselective synthesis, and most of them are focused on the transformations of allenes.…”

Copper-Catalyzed Ring-Opening Defluoroborylation of gem-Difluorinated Cyclobutenes: A General Route to Bifunctional 1,3-Dienes and Their Applications

“…This chemistry was initially discovered by Hoveyda and coworkers in 2011, who reported a copper-catalyzed reaction of α-CF 3 -styrenes with bis­(pinacolato)­diborane (B 2 pin 2 ) to produce difluoroallyl boronates . Subsequently, the stereoselectivity and the substrate scope of this defluorinative borylation were intensively studied by the research groups of Ito, Shi, Cao, and others, which provides a good avenue for the generation of B,F-bifunctional molecules with a great diversity of substitution patterns (Scheme c).…”