The Baeyer-Villiger oxidation of ketones to the corresponding esters or lactones is a valuable transformation that has been upgraded several times over the last century, from the original use of monopersulfuric acid as oxidant to more atom efficient and environmentally friendly oxidants such as hydrogen peroxide. The latter requires activation with organometallic complexes to explicate its oxidizing power. The catalytic version of the reaction can be achieved with several transition metal catalysts, but major differences are present among the various catalysts proposed in terms of scope of the reaction. In particular, most of the catalytic systems are active towards four-membered ring ketones leading to the corresponding substituted gamma-butyro-lactones. Pt(II) complexes characterized by the employment of chelating diphosphines turned out to be the most efficient in catalyzing the BV oxidation of a wider range of substrates, in particular cyclohexanones are Suitable substrates and acyclic ketones can be converted into the corresponding esters, albeit with low turnover. As long as organometallic catalyzed BV reaction is concerned, Pt(II) catalysts show the most versatile activity and selectivity. Such peculiar features are the result of the unique electronic properties of such metal combined with an easily tailored soft Lewis acid character modulated by the proper choice of the ancillary ligands. The enantioselective version of the reaction benefits from these properties and the compatibility of Pt(II) species with water enabled the development of asymmetric catalytic BV reactions in water aided by the presence of micelles as dynamic self-assembled environments. (C) 2009 Elsevier B.V. All rights reserved.
The Baeyer-Villiger oxidation of ketones: A paradigm for the role of soft Lewis acidity in homogeneous catalysis
MICHELIN, RINO;SGARBOSSA, PAOLO;
2010
Abstract
The Baeyer-Villiger oxidation of ketones to the corresponding esters or lactones is a valuable transformation that has been upgraded several times over the last century, from the original use of monopersulfuric acid as oxidant to more atom efficient and environmentally friendly oxidants such as hydrogen peroxide. The latter requires activation with organometallic complexes to explicate its oxidizing power. The catalytic version of the reaction can be achieved with several transition metal catalysts, but major differences are present among the various catalysts proposed in terms of scope of the reaction. In particular, most of the catalytic systems are active towards four-membered ring ketones leading to the corresponding substituted gamma-butyro-lactones. Pt(II) complexes characterized by the employment of chelating diphosphines turned out to be the most efficient in catalyzing the BV oxidation of a wider range of substrates, in particular cyclohexanones are Suitable substrates and acyclic ketones can be converted into the corresponding esters, albeit with low turnover. As long as organometallic catalyzed BV reaction is concerned, Pt(II) catalysts show the most versatile activity and selectivity. Such peculiar features are the result of the unique electronic properties of such metal combined with an easily tailored soft Lewis acid character modulated by the proper choice of the ancillary ligands. The enantioselective version of the reaction benefits from these properties and the compatibility of Pt(II) species with water enabled the development of asymmetric catalytic BV reactions in water aided by the presence of micelles as dynamic self-assembled environments. (C) 2009 Elsevier B.V. All rights reserved.
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