The Baeyer-Villiger oxidation of some cyclic ketones as a potential entry to naturally occurring lactones is reported in the presence of a variety of platinum(II) complexes as catalysts. The reaction is accomplished using hydrogen peroxide as oxidant and is tested in a discontinuous and semicontinuous fashion. The stereochemistry of the catalyzed transformation has been determined, and it is found that the reaction proceeds with retention of configuration at the migrating carbon atom. Chiral catalysts of the type [(P-P*)Pt(CF3)-(solv)]+ and (P-P*)Pt(2-van) (P-P* = various chiral diphosphines; 2-van = the dianion of 2-vanillin) have been synthesized and characterized. While the mechanism of action of the former complexes is already known, the latter require 1 equiv of HClO4 to become catalytically active. This reaction has been investigated synthetically and spectroscopically by 31P{1H} NMR and IR and results in the formation of a new cationic Pt-carbonyl species. The asymmetric Baeyer-Villiger oxidation of a variety of racemic mixtures of chiral ketones results in a kinetic resolution leading to chiral lactones with ee up to 58%. © 1994, American Chemical Society. All rights reserved.

Platinum-Catalyzed Oxidations with Hydrogen Peroxide: Enantiospecific Baeyer-Villiger Oxidation of Cyclic Ketones

PINNA, Francesco;STRUKUL, Giorgio
1994-01-01

Abstract

The Baeyer-Villiger oxidation of some cyclic ketones as a potential entry to naturally occurring lactones is reported in the presence of a variety of platinum(II) complexes as catalysts. The reaction is accomplished using hydrogen peroxide as oxidant and is tested in a discontinuous and semicontinuous fashion. The stereochemistry of the catalyzed transformation has been determined, and it is found that the reaction proceeds with retention of configuration at the migrating carbon atom. Chiral catalysts of the type [(P-P*)Pt(CF3)-(solv)]+ and (P-P*)Pt(2-van) (P-P* = various chiral diphosphines; 2-van = the dianion of 2-vanillin) have been synthesized and characterized. While the mechanism of action of the former complexes is already known, the latter require 1 equiv of HClO4 to become catalytically active. This reaction has been investigated synthetically and spectroscopically by 31P{1H} NMR and IR and results in the formation of a new cationic Pt-carbonyl species. The asymmetric Baeyer-Villiger oxidation of a variety of racemic mixtures of chiral ketones results in a kinetic resolution leading to chiral lactones with ee up to 58%. © 1994, American Chemical Society. All rights reserved.
1994
13
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/13058
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 159
  • ???jsp.display-item.citation.isi??? ND
social impact