Preparation of (Z)-1-fluoro-1-alkenyl carboxylates, carbonates and carbamates through chromium mediated transformation of dibromofluoromethylcarbinyl esters and the reactivity as double acyl group donors

CrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl2/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.

Graphical abstractCrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters provided 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Efficient synthesis of (Z)-1-fluoro-1-alkenyl carboxylates, carbonates and carbamates. ► CrCl2/Mn-mediated transformation of dibromofluorocarbinyl esters via chromium fluorocarbene complex. ► Stepwise double acyl transfer reaction of 1-fluoro-1-alkenyl esters with nucleophies including bifunctional nucleopile such as ethylene diamine derivative.