Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction

Scott E. Denmark, Zachery D. Matesich, Son T. Nguyen, Selena Milicevic Sephton

Research output: Contribution to journalArticle

Abstract

The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.

Original languageEnglish (US)
Pages (from-to)23-48
Number of pages26
JournalJournal of Organic Chemistry
Volume83
Issue number1
DOIs
StatePublished - Jan 5 2018

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Allylation
Nucleophiles
Water gas shift
Aldehydes
Carbon
Ruthenium
Carbon Monoxide
Amines
Modulation
Water

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction. / Denmark, Scott E.; Matesich, Zachery D.; Nguyen, Son T.; Milicevic Sephton, Selena.

In: Journal of Organic Chemistry, Vol. 83, No. 1, 05.01.2018, p. 23-48.

Research output: Contribution to journalArticle

Denmark, Scott E. ; Matesich, Zachery D. ; Nguyen, Son T. ; Milicevic Sephton, Selena. / Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction. In: Journal of Organic Chemistry. 2018 ; Vol. 83, No. 1. pp. 23-48.
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