Pd‐Catalyzed Selective Carbonylation of gem‐Difluoroalkenes: A Practical Synthesis of Difluoromethylated Esters

The first catalyst for the alkoxycarbonylation of gem‐difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac)₂/1,2‐bis((di‐tert‐butylphosphan‐yl)methyl)benzene (btbpx) ( L4 ) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.