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Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

Author

Listed:
  • Da-Chang Bai

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Fei-Le Yu

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Wan-Ying Wang

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Di Chen

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Hao Li

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Qing-Rong Liu

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Chang-Hua Ding

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

  • Bo Chen

    (Baker Laboratory, Cornell University)

  • Xue-Long Hou

    (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences
    Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences)

Abstract

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3’]-reductive elimination.

Suggested Citation

  • Da-Chang Bai & Fei-Le Yu & Wan-Ying Wang & Di Chen & Hao Li & Qing-Rong Liu & Chang-Hua Ding & Bo Chen & Xue-Long Hou, 2016. "Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism," Nature Communications, Nature, vol. 7(1), pages 1-11, June.
    • Handle: RePEc:nat:natcom:v:7:y:2016:i:1:d:10.1038_ncomms11806
    DOI: 10.1038/ncomms11806
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    Cited by:

    1. Shuai Huang & Fei-Fei Tong & Da-Chang Bai & Gao-Peng Zhang & Yang-Jie Jiang & Bo Zhang & Xuebing Leng & Ying-Long Guo & Xiao-Long Wan & Xingang Zhang & Chang-Hua Ding & Xue-Long Hou, 2021. "Regio- and enantioselective umpolung gem-difluoroallylation of hydrazones via palladium catalysis enabled by N-heterocyclic carbene ligand," Nature Communications, Nature, vol. 12(1), pages 1-9, December.

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