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Issue 6, 2018
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Regioselective Simmons–Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis

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Abstract

A [i−PrPDI]CoBr2 complex (PDI = pyridine-diimine) catalyzes Simmons–Smith-type reductive cyclopropanation reactions using CH2Br2 in combination with Zn. In contrast to its non-catalytic variant, the cobalt-catalyzed cyclopropanation is capable of discriminating between alkenes of similar electronic properties based on their substitution patterns: monosubstituted > 1,1-disubstituted > (Z)-1,2-disubstituted > (E)-1,2-disubstituted > trisubstituted. This property enables synthetically useful yields to be achieved for the monocyclopropanation of polyalkene substrates, including terpene derivatives and conjugated 1,3-dienes. Mechanistic studies implicate a carbenoid species containing both Co and Zn as the catalytically relevant methylene transfer agent.

Graphical abstract: Regioselective Simmons–Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis

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Publication details

The article was received on 10 Nov 2017, accepted on 23 Dec 2017 and first published on 02 Jan 2018


Article type: Edge Article
DOI: 10.1039/C7SC04861K
Citation: Chem. Sci., 2018,9, 1604-1609
  • Open access: Creative Commons BY license
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    Regioselective Simmons–Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis

    J. Werth and C. Uyeda, Chem. Sci., 2018, 9, 1604
    DOI: 10.1039/C7SC04861K

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