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 b...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 R_(2)P(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,2,1-hydrophosphorylation 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.展开更多
The synthesis of phosphine compounds through the addition reaction of H-[P(O)]species to olefins and alkynes has been extensively studied.Two different mechanisms of the addition of H-[P(O)]species to non-activated al...The synthesis of phosphine compounds through the addition reaction of H-[P(O)]species to olefins and alkynes has been extensively studied.Two different mechanisms of the addition of H-[P(O)]species to non-activated alkyne are mainly summarized.One is the oxidative addition-migration insertion-reductive elimination mechanism,namely the Chalk-Harrod type mechanism,and the other is the proton transfer-reductive elimination mechanism.This review elaborates on the specific steps of each mechanism,and discusses experimental and computational evidence supporting these steps.Additionally,a few other types of mechanisms are briefly mentioned.The mechanism of H-[P(O)]reaction with relevant conjugated dienes was also involved when closely related.展开更多
基金Financial support from Dalian Outstanding Young Scientific Talent(No.2020RJ05)the National Natural Science Foundation of China(Nos.22071239,21971234)。
文摘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 R_(2)P(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,2,1-hydrophosphorylation 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.
文摘The synthesis of phosphine compounds through the addition reaction of H-[P(O)]species to olefins and alkynes has been extensively studied.Two different mechanisms of the addition of H-[P(O)]species to non-activated alkyne are mainly summarized.One is the oxidative addition-migration insertion-reductive elimination mechanism,namely the Chalk-Harrod type mechanism,and the other is the proton transfer-reductive elimination mechanism.This review elaborates on the specific steps of each mechanism,and discusses experimental and computational evidence supporting these steps.Additionally,a few other types of mechanisms are briefly mentioned.The mechanism of H-[P(O)]reaction with relevant conjugated dienes was also involved when closely related.
