4.7 Article

Co-complexes derived from alkene insertion to alkyne-dicobaltpentacarbonyl complexes: Insight into the regioselectivity of Pauson-Khand reactions of cyclopropenes

Journal

JOURNAL OF ORGANIC CHEMISTRY
Volume 73, Issue 16, Pages 6137-6141

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jo800776z

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Funding

  1. NIGMS NIH HHS [R01 GM068640-05, R01 GM068640-01A1, R01 GM068640-04, GM068640-01, R01 GM068640-03, R01 GM068640-02, R01 GM068640] Funding Source: Medline

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Described are the X-ray crystallographic and spectral properties of Co-complexes that were isolated from two Pauson-Khand reactions of chiral cyclopropenes. These are the first examples of isolated Co-complexes derived from the putative alkene-insertion intermediates of Pauson-Khand reactions. The binuclear Co-complexes are coordinated to mu-bonded, five-carbon flyover carbene ligands. It is proposed that the complexes result from cyclopropane fragmentation subsequent to alkene insertion. The observation of these metal complexes provides a rationale for the origin of regioselectivity in Pauson-Khand reactions of cyclopropenes.

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