Nickel-catalysed asymmetric hydromonofluoromethylation of 1,3-enynes for enantioselective construction of monofluoromethyl-tethered chiral allenes

An unprecedented nickel-catalysed enantioselective hydromonofluoromethylation of 1,3-enynes is developed, allowing the diverse access to monofluoromethyl-tethered axially chiral allenes, including the challenging deuterated monofluoromethyl (CD2F)-tethered ones that are otherwise inaccessible. It represents the first asymmetric 1,4-hydrofunctionalization of 1,3-enynes using low-cost asymmetric nickel catalysis, thus opening a new avenue for the activation of 1,3-enynes in reaction development. The utility is further verified by its broad substrate scope, good functionality tolerance, mild conditions, and diversified product elaborations toward other valuable fluorinated structures. Mechanistic experiments and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity. An unprecedented nickel-catalysed enantioselective hydromonofluoromethylation of 1,3-enynes is developed, allowing access to valuable monofluoromethyl-tethered chiral allenes that are otherwise inaccessible.

Automated summary

This study developed an unprecedented nickel-catalyzed enantioselective hydromonofluoromethylation reaction, enabling the synthesis of valuable monofluoromethyl-tethered chiral allenes that were previously inaccessible. The method exhibits broad substrate scope, good functionality tolerance, mild reaction conditions, and the ability to construct other valuable fluorinated compounds.