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. 2013 Nov 6;135(44):16320-3.
doi: 10.1021/ja4087193. Epub 2013 Oct 24.

Ruthenium catalyzed hydrohydroxyalkylation of isoprene with heteroaromatic secondary alcohols: isolation and reversible formation of the putative metallacycle intermediate

Boyoung Y Park  1 , T Patrick Montgomery, Victoria J Garza, Michael J Krische
Affiliations

Ruthenium catalyzed hydrohydroxyalkylation of isoprene with heteroaromatic secondary alcohols: isolation and reversible formation of the putative metallacycle intermediate

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

Erratum in

  • J Am Chem Soc. 2014 Aug 20;136(33):11848

Abstract

Heteroaromatic secondary alcohols react with isoprene to form products of hydrohydroxyalkylation in the presence of ruthenium(0) catalysts generated from Ru3(CO)12 and tricyclohexylphosphine, enabling direct conversion of secondary to tertiary alcohols in the absence of premetalated reagents or stoichiometric byproducts. The putative oxaruthenacycle intermediate has been isolated and characterized, and reversible metallacycle formation has been demonstrated.

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Figures

Figure 1
Figure 1
The LUMO-lowering effect of aromatic heterocycles promotes oxidative coupling pathways in catalytic hydrogenative and transfer hydrogenative C-C coupling.
Figure 2
Figure 2
Single crystal X-ray diffraction data of the oxaruthenacycle Ia-π-allyl derived from Ru3(CO)12, 2-benzoylpyridine oxo-1a and isoprene 2a. Displacement ellipsoids are scaled to the 50% probability level. Hydrogen atoms have been omitted for clarity.
Figure 3
Figure 3
Conversion of Ib-π-allyl to Ia-π-allyl corroborates reversible formation of the oxaruthenacycle intermediate.
Scheme 1
Scheme 1
Postulated catalytic mechanism involving diene-carbonyl oxidative coupling.
See this image and copyright information in PMC

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