Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 7, Pages 2063-2071Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200902928
Keywords
heterogeneous catalysis; homogeneous catalysis; insertion; nickel; stereoselectivity; vinyl sulfides
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Funding
- Russian Foundation for Basic Research [10-03-00370]
- Division of Chemistry and Material Sciences of RAS [1]
- [MK-1085.2008.3]
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The present study reports the evidence for the multiple carbon-carbon bond insertion into the metal-heteroatom bond via a five-coordinate metal complex. Detailed analysis of the model catalytic reaction of the carbon-sulfur (C-S) bond formation unveiled the mechanism of metal-mediated alkyne insertion: a new pathway of C-S bond formation without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this pathway alkyne insertion into the metal-sulfur bond led to the formation of intermediate metal complex capable of direct C-S reductive elimination. In contrast, an intermediate metal complex formed through alkyne insertion through the traditional pathway involving preliminary ligand dissociation suffered from improper geometry configuration, which may block the whole catalytic cycle. A new catalytic system was developed to solve the problem of stereoselective S-S bond addition to internal alkynes and a cost-efficient Ni-catalyzed synthetic procedure is reported to furnish formation of target vinyl sulfides with high yields (up to 99%) and excellent Z/E selectivity (>99:1).
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