Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 7, Pages 1584-1590Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201603758
Keywords
allenes; cross-coupling; density functional calculations; nickel; reaction mechanisms
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Funding
- MINECO [CTQ2013-42806-R]
- UAM
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We describe the unprecedented formation of allenes by Ni-catalyzed cross-coupling of propargyl bromides with alkylzinc halides. The reaction regioselectivity is complementary to the previously reported formation of propargyl-coupled compounds. Experiments support the formation of Ni-I complexes as the active species and the participation of radical intermediates. Kinetic studies showed that the reaction is first order with respect to the electrophile, zero-order with respect to the nucleophile (fast transmetalation), and one-half order with respect to the metal catalyst. Mechanistic studies support a bimetallic Ni-I-based pathway that involves fast homolytic cleavage of the C-Br bond by an alkyl-Ni-I complex, followed by radical coordination to NiI that determines the observed regioselectivity.
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