Ni-catalyzed regiodivergent hydrophosphorylation of enynes

A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earthabundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)(2)P(O)-Ni-H or R2P(O)O-Ni-H species, respectively. Under the Ni/Xantphos catalysis, 4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition. By employing an additional Pd-H catalysis, 2,1hydrophosphorylation is also an accessible task in one-pot reaction. Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation. This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps. (c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)(2)P(O)-Ni-H or R2P(O)O-Ni-H species, respectively. This research highlights the ability to access different regioisomers by diverting common elementary reaction steps.