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

The first catalyst system 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 wide range of difluoromethylated esters in high yields with good to excellent regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.

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