Synlett 1994; 1994(7): 465-470
DOI: 10.1055/s-1994-22893
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Organonickel Chemistry in Organic Synthesis. Some Applications of Alkyl and Metalacyclic Derivatives

J. Cámpora* , M. Paneque, M. L. Poveda, E. Carmona
  • *Departamento de Química Inorgánica-Instituto de Ciencia de Materiales, Universidad de Sevilla-CSIC, Apdo 553, 41071 Sevilla, Spain
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Publication History

Publication Date:
18 September 2002 (online)

The Ni-C bonds of stable, square-planar Ni(II)-alkyl and metalacyclic complexes, that contain the strongly basic PMe3 group as the stabilizing ligand, are shown to exhibit a very rich insertion chemistry toward a number of unsaturated molecules (CO, CNBut, alkynes, CS2, CSNPh, ...). Heterocumulenes CXY (e. g. CO2, CS2, ...) regioselectively insert into the Ni-aryl bond of the nickelacycle (Me3P)2Ni(CH2CMe2-o-C6H4) 3 to yield unstable intermediate species, able to undergo the subsequent insertion of CO or CNBut.This sequential insertion chemistry proves to be particularly rewarding and allows the synthesis of a number of sulfur-containing organic heterocycles. l. Introduction 2. Formation of Dimeric α,β-Butenolides by Sequential Insertion of CO and PhC≡CH into Ni-C Bonds 3. Synthesis and Insertion Chemistry of the Nickelacyclopentene complex (Me3P)2Ni(CH2CMe2-o-C6H4) 3.1. Preparative Studies 3.2. Synthesis of 1,2-Dihydronaphthalenes 3.3. Insertion Reactions with CO, CH2O and CNBut 3.4. Heterocumulene Insertion 4. Conclusions

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