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

Da Chang Bai, Fei Le Yu, Wan Ying Wang, Di Chen, Hao Li, Qing Rong Liu, Chang Hua Ding, Bo Chen, Xue Long Hou

Research output: Contribution to journalArticle

21 Citations (Scopus)

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.

Original languageEnglish (US)
Article number11806
JournalNature communications
Volume7
DOIs
StatePublished - Jun 10 2016

Fingerprint

Palladium
carbenes
Ketones
ketones
reagents
palladium
Synthetic Chemistry Techniques
Catalysis
Transition metals
Density functional theory
Substitution reactions
Metals
Oxygen
Ligands
products
attack
catalysis
Substrates
elimination
transition metals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Bai, Da Chang ; Yu, Fei Le ; Wang, Wan Ying ; Chen, Di ; Li, Hao ; Liu, Qing Rong ; Ding, Chang Hua ; Chen, Bo ; Hou, Xue Long. / Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism. In: Nature communications. 2016 ; Vol. 7.
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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.",
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Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism. / Bai, Da Chang; Yu, Fei Le; Wang, Wan Ying; Chen, Di; Li, Hao; Liu, Qing Rong; Ding, Chang Hua; Chen, Bo; Hou, Xue Long.

In: Nature communications, Vol. 7, 11806, 10.06.2016.

Research output: Contribution to journalArticle

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AU - Yu, Fei Le

AU - Wang, Wan Ying

AU - Chen, Di

AU - Li, Hao

AU - Liu, Qing Rong

AU - Ding, Chang Hua

AU - Chen, Bo

AU - Hou, Xue Long

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