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

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 beta-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. As a result, 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.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [3]
  1. Chinese Academy of Sciences, Shanghai (China). State Key Laboratory of Organometallic Chemistry, Shanghai Instit. of Organic Chemistry
  2. Cornell University, Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology, Baker Laboratory
  3. Chinese Academy of Sciences, Shanghai (China). State Key Laboratory of Organometallic Chemistry, Shanghai Instit. of Organic Chemistry and Shanghai Hong Kong Joint Laboratory in Chemical Synthesis
Publication Date:
OSTI Identifier:
1287338
Grant/Contract Number:
SC0001057
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Chinese Academy of Sciences, Shanghai (China)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY asymmetric conjugate addition; chiral phosphine-ligands; c bond formation; allylpalladium complexes; reductive elimination; alpha-allylation; alkylation; construction; derivatives; metathesis