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. 2009 May 6;131(17):6076-7.
doi: 10.1021/ja901212h.

A general and efficient catalyst system for a Wacker-type oxidation using TBHP as the terminal oxidant: application to classically challenging substrates

Brian W Michel  1 , Andrew M Camelio, Candace N Cornell, Matthew S Sigman
Affiliations

A general and efficient catalyst system for a Wacker-type oxidation using TBHP as the terminal oxidant: application to classically challenging substrates

Brian W Michel et al. J Am Chem Soc. .

Abstract

Utilizing the rapidly synthesized Quinox ligand and commercially available aqueous TBHP, a Wacker-type oxidation has been developed, which efficiently converts the traditionally challenging substrate class of protected allylic alcohols to the corresponding acyloin products. Additionally, the catalytic system is general for several other substrate classes, converting terminal olefins to methyl ketones, with short reaction times. The system is scalable (20 mmol) and can be performed with a reduced catalyst loading of 1 mol%. Enantioenriched substrates undergo oxidation with complete retention of enantiomeric excess.

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Figures

Figure 1
Figure 1
(A) Poor selectivity for protected allylic alcohols under Tsuji-Wacker conditions and (B) two step oxymercuration-transmetallation for selective oxidation of protected allylic alcohols.
Figure 2
Figure 2
Evaluation of bidentate ligands and solvent.
Scheme 1
Scheme 1
(A) Proposed coordination of protected allylic alcohols and (B) our hypothesis for TBHP-mediated Wacker-type reaction utilizing a bidentate ligand to block coordination of oxygen atom.
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