[(NHC)NiIIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)NiII]‐Assisted C−C Rearrangement

A cross‐hydroalkenylation/rearrangement cascade (HARC), using a cyclopropene and alkyne as substrate pairs, was achieved for the first time by using new [(NHC)Ni(allyl)]BArF catalysts (NHC=N‐heterocyclic carbenes). By controlling the (NHC)NiIIH relative insertion reactivity with cyclopropene and alk...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-04, Vol.58 (17), p.5702-5706
Main Authors: Huang, Jian‐Qiang, Ho, Chun‐Yu
Format: Article
Language:English
Subjects:
Alkynes
Carbenes
Catalysis
Catalysts
Chemical synthesis
Cyclopentadiene
dienes
N-heterocyclic carbenes
nickel
Organic compounds
rearrangements
Substrates
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Summary:A cross‐hydroalkenylation/rearrangement cascade (HARC), using a cyclopropene and alkyne as substrate pairs, was achieved for the first time by using new [(NHC)Ni(allyl)]BArF catalysts (NHC=N‐heterocyclic carbenes). By controlling the (NHC)NiIIH relative insertion reactivity with cyclopropene and alkyne, a broad scope of cyclopentadienes was obtained with highly selectively. The structural features of the new (NHC)NiII catalyst were important for the success of the reaction. The mild reaction conditions employed may serve as an entry for exploring (NHC)NiII‐assisted vinylcyclopropane rearrangement reactivity. HARC: Functionalized cyclopentadienes (3) were prepared by a catalytic cross‐hydroalkenylation/rearrangement cascade (HARC). The broad substrate scope with respect to the alkynes 1 and cyclopropenes 2 is a result of the optimal insertion reactivity and high rearrangement reactivity enabled by new (NHC)NiII catalysts. The method avoids the use of vinyl metal carbenoids.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201901255