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Recently, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences has made progress in the research on bimetallic catalyzed olefin carbonylation reaction, realizing the highly selective conversion of long-chain aliphatic olefins, and obtaining the "Markovian rule" branched-chain carboxylation.
ester product
.
The research team designed and synthesized a class of carbazolyl phosphine ligands (PN) containing bipyridyl structural units, which were coordinated with different metals through bipyridyl and phosphine sites respectively, in order to achieve bimetallic synergistic enhancement of the regioselectivity of the reaction.
control
.
Based on the catalytic system composed of palladium-manganese bimetals and PN ligands, they achieved a highly selective conversion of long-chain aliphatic olefins and obtained "Martens rule" branched-chain carboxylate products
.
Both aliphatic and aromatic olefins can generate branched carboxylic acid esters with high selectivity
.
In addition, different kinds of alcohols also have good substrate suitability
.
The research team studied the mechanism of this reaction through experiments and theoretical calculations
.
Based on the experimental results, they proposed a possible mechanism for the palladium-manganese bimetallic catalyzed alkoxycarbonylation reaction
.
Alkoxycarbonylation is an important method for the preparation of ester compounds
.
Usually, the alkoxycarbonylation reaction uses transition metal as catalyst (such as palladium complex), takes olefin as raw material, carbon monoxide as carbonyl source, alcohol as hydrogen source and nucleophile reaction to prepare ester products, which has high product value, Atomic economy and other advantages
.
Long-chain aliphatic olefins are a wide variety of chemicals that can be converted into various biologically active compounds and important pharmaceutical intermediates
.
The branch-selective (Markovnikov rule) alkoxycarbonylation catalytic systems of long-chain aliphatic olefins are relatively few
.
Aliphatic branched-chain ester compounds are widely used in pharmaceuticals, polymer materials, fragrances and other fields
.
Therefore, it is of great significance to develop a general and highly branched-selective alkoxycarbonylation reaction system suitable for long-chain aliphatic olefins
.