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Ruthenium-Catalyzed C−C Bond Forming Transfer Hydrogenation: Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Employing Acyclic 1,3-Dienes as Surrogates to Preformed Allyl Metal Reagents
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    Ruthenium-Catalyzed C−C Bond Forming Transfer Hydrogenation: Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Employing Acyclic 1,3-Dienes as Surrogates to Preformed Allyl Metal Reagents
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    Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2008, 130, 20, 6338–6339
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    https://doi.org/10.1021/ja801213x
    Published April 29, 2008
    Copyright © 2008 American Chemical Society

    Abstract

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    Under the conditions of ruthenium-catalyzed transfer hydrogenation, commercially available acyclic 1,3-dienes, butadiene, isoprene, and 2,3-dimethylbutadiene, couple to benzylic alcohols 1a6a to furnish products of carbonyl crotylation 1b6b, carbonyl isoprenylation 1c6c, and carbonyl reverse 2-methyl prenylation 1d6d. Under related transfer hydrogenation conditions employing isopropanol as terminal reductant, isoprene couples to aldehydes 7a9a to furnish identical products of carbonyl isoprenylation 1c3c. Thus, carbonyl allylation is achieved from the alcohol or the aldehyde oxidation level in the absence of preformed allyl metal reagents. Coupling to aliphatic alcohols (isoprene to 1-nonanol, 65% isolated yield) and allylic alcohols (isoprene to geraniol, 75% isolated yield) also is demonstrated. Isotopic labeling studies corroborate a mechanism involving hydrogen donation from the reactant alcohol or sacrificial alcohol (i-PrOH).

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    Cite this: J. Am. Chem. Soc. 2008, 130, 20, 6338–6339
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    Published April 29, 2008
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