Palladium-catalyzed enantioselective oxidation of alcohols: a dramatic rate acceleration by Cs2CO3/t-BuOH.
نویسندگان
چکیده
[reaction: see text] The addition of Cs(2)CO(3) and t-BuOH provides a dramatic rate acceleration in the palladium-catalyzed aerobic oxidative kinetic resolution of secondary alcohols while maintaining the selectivity of the process.
منابع مشابه
Palladium-catalyzed enantioselective oxidation of chiral secondary alcohols: access to both enantiomeric series.
Palladium-Catalyzed Enantioselective Oxidation of Chiral Secondary Alcohols: Access to Both Enantiomeric Series David C. Ebner, Raissa M. Trend, Cédric Genet, Matthew J. McGrath, Peter O’Brien*, and Brian M. Stoltz* The Arnold and Mabel Beckman Laboratories of Chemical Synthesis Division of Chemistry and Chemical Engineering, California Institute of Technology Pasadena, California 91125 (USA) D...
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متن کاملPd-catalyzed enantioselective aerobic oxidation of secondary alcohols: applications to the total synthesis of alkaloids.
Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility o...
متن کاملMechanism of the aerobic oxidation of alcohols by palladium complexes of N-heterocyclic carbenes.
Quantum mechanics (B3LYP density functional theory) combined with solvation (Poisson-Boltzmann polarizable continuum solvent model) was used to investigate six mechanisms for the aerobic oxidation of alcohols catalyzed by (NHC)Pd(carboxylate)(2)(H(2)O) complexes (NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Of these, we find that "reductive beta-hydride elimination", in which the be...
متن کاملThe palladium-catalyzed aerobic kinetic resolution of secondary alcohols: reaction development, scope, and applications.
The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbona...
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عنوان ژورنال:
- Organic letters
دوره 5 6 شماره
صفحات -
تاریخ انتشار 2003