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. 2015 Jun 24;137(24):7652-5.
doi: 10.1021/jacs.5b04688. Epub 2015 Jun 12.

A Metallacycle Fragmentation Strategy for Vinyl Transfer from Enol Carboxylates to Secondary Alcohol C-H Bonds via Osmium- or Ruthenium-Catalyzed Transfer Hydrogenation

Boyoung Y Park  1 , Tom Luong  1 , Hiroki Sato  1 , Michael J Krische  1
Affiliations

A Metallacycle Fragmentation Strategy for Vinyl Transfer from Enol Carboxylates to Secondary Alcohol C-H Bonds via Osmium- or Ruthenium-Catalyzed Transfer Hydrogenation

Boyoung Y Park et al. J Am Chem Soc. .

Abstract

A strategy for catalytic vinyl transfer from enol carboxylates to activated secondary alcohol C-H bonds is described. Using XPhos-modified ruthenium(0) or osmium(0) complexes, enol carboxylate-carbonyl oxidative coupling forms transient β-acyloxy-oxametallacycles, which eliminate carboxylate to deliver allylic ruthenium(II) or osmium(II) alkoxides. Reduction of the metal(II) salt via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-H vinylation and regenerates ketone and zero-valent catalyst.

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Figures

Scheme 1
Scheme 1
Convergent Methods for the Synthesis of Allylic Alcohols through Vinyl Transfer.
Scheme 2
Scheme 2
Proposed General Catalytic Mechanism Involving Oxidative Coupling-Metallacycle Fragmentation.
See this image and copyright information in PMC

References

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