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

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2008 May 1

PMID 18444617

Citations 66

Authors

Fumitoshi Shibahara

John F Bower

Michael J Krische

Affiliations

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Abstract

Under the conditions of ruthenium-catalyzed transfer hydrogenation, commercially available acyclic 1,3-dienes, butadiene, isoprene, and 2,3-dimethylbutadiene, couple to benzylic alcohols 1a-6a to furnish products of carbonyl crotylation 1b-6b, carbonyl isoprenylation 1c-6c, and carbonyl reverse 2-methyl prenylation 1d-6d. Under related transfer hydrogenation conditions employing isopropanol as terminal reductant, isoprene couples to aldehydes 7a-9a to furnish identical products of carbonyl isoprenylation 1c-3c. 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).

Citing Articles

Catalytic Enantioselective C-C Coupling of Alcohols for Polyketide Total Synthesis beyond Chiral Auxiliaries and Premetalated Reagents.

Wu J, Verboom K, Krische M Chem Rev. 2024; 124(24):13715-13735.

PMID: 39642170 PMC: 11826517. DOI: 10.1021/acs.chemrev.4c00858.

β-Hydroxy Esters as Malonic Semialdehyde Proelectrophiles in Enantioselective Butadiene-Mediated Crotylation: Total Synthesis of Octalactins A and B.

Wu J, Krische M Org Lett. 2024; 26(22):4830-4834.

PMID: 38804715 PMC: 11444018. DOI: 10.1021/acs.orglett.4c01644.

Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C-C Couplings via Hydrogen Transfer.

Shezaf J, Santana C, Ortiz E, Meyer C, Liu P, Sakata K J Am Chem Soc. 2024; 146(12):7905-7914.

PMID: 38478891 PMC: 11446212. DOI: 10.1021/jacs.4c01857.

Intermolecular Metal-Catalyzed C‒C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents.

Spinello B, Strong Z, Ortiz E, Evarts M, Krische M ACS Catal. 2024; 13(16):10976-10987.

PMID: 38464997 PMC: 10923551. DOI: 10.1021/acscatal.3c02209.

Carbonyl Allylation and Crotylation: Historical Perspective, Relevance to Polyketide Synthesis, and Evolution of Enantioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer Processes.

Ortiz E, Saludares C, Wu J, Cho Y, Santana C, Krische M Synthesis (Stuttg). 2023; 55(10):1487-1496.

PMID: 37841289 PMC: 10569400. DOI: 10.1055/s-0042-1751420.

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