Acid-Free Nickel Catalyst for Stereo- and Regioselective Hydrophosphorylation of Alkynes: Synthetic Procedure and Combined Experimental and Theoretical Mechanistic Study

被引：76

作者：

Ananikov, Valentine P. ^{[1
]}

Khemchyan, Levon L. ^{[1
]}

Beletskaya, Irina P. ^{[2
]}

Starikova, Zoya A. ^{[3
]}

机构：

[1] Russian Acad Sci, Zelinsky Inst Organ Chem, Moscow 119991, Russia

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia

[3] Russian Acad Sci, Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2010年 / 352卷 / 17期

基金：

俄罗斯基础研究基金会;

关键词：

alkynes; homogeneous catalysis; nickel complexes; phosphorylation; selectivity; MOLECULAR-ORBITAL METHODS; EFFECTIVE CORE POTENTIALS; CARBON BOND FORMATION; GAUSSIAN-TYPE BASIS; ENANTIOSELECTIVE SYNTHESIS; TERMINAL ALKYNES; PHOSPHONIC ACID; INTRAMOLECULAR HYDROPHOSPHINATION/CYCLIZATION; ACRYLONITRILE HYDROPHOSPHINATION; INTERMOLECULAR HYDROALKOXYLATION;

D O I：

10.1002/adsc.201000606

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The nickel catalyst prepared in situ from nickel bis(acetylacetonate) [Ni(acac)(2)] precursor and bis(diphenylphosphino) ethane (DPPE) ligand has shown excellent performance in the hydrophosphorylation of alkynes. Markovnikov-type regioselective addition to terminal alkynes and stereoselective addition to internal alkynes were carried out with high selectivity without an acidic co-catalyst (in contrast to the palladium/acid catalytic system). Various H-phosphonates and alkynes reacted smoothly in the developed catalytic system with up to 99% yield. The mechanisms of catalyst activation and C-P bond formation were revealed by experimental (NMR, ESI-MS, X-ray) and theoretical (density functional calculations) studies. Two different pathways of the alkyne insertion in the coordination sphere of the metal are reported for the first time.

引用

页码：2979 / 2992

页数：14

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