RUTHENIUM(II)-CATALYZED OPPENAUER-TYPE OXIDATION OF SECONDARY ALCOHOLS

Citation
Mls. Almeida et al., RUTHENIUM(II)-CATALYZED OPPENAUER-TYPE OXIDATION OF SECONDARY ALCOHOLS, Chemistry, 2(12), 1996, pp. 1533-1536
Citations number
48
Categorie Soggetti
Chemistry
Journal title
ISSN journal
09476539
Volume
2
Issue
12
Year of publication
1996
Pages
1533 - 1536
Database
ISI
SICI code
0947-6539(1996)2:12<1533:ROOOSA>2.0.ZU;2-T
Abstract
Highly efficient ruthenium-catalyzed Oppenauer-type oxidations of seco ndary alcohols to ketones have been developed. The catalytic system co nsists of [(PPh(3))(3)RuCl2] (1) and K2CO3 or [(C(4)Ph(4)COHOCC(4)Ph(4 ))(mu-H)(CO)(4)Ru-2] (2) in refluxing acetone. The catalytic reaction is of high efficiency and permits a catalyst:substrate ratio of 1:1000 at 56 degrees C. In some cases the initial turnover rate exceeds 1500 h(-1). The reaction was found to be general and compatible with doubl e bonds and oxidation-sensitive aromatics. With some allylic alcohols, isomerization to saturated ketones took place. The reaction proceeds by ruthenium-catalyzed dehydrogenation of the alcohol and subsequent h ydrogen transfer to acetone. No primary kinetic isotope effect was obs erved for the catalytic reaction when alpha-deuterated 1-phenylethanol was employed as substrate (k(H)/k(D) = 1.1); this shows that beta-hyd ride elimination from a ruthenium alkoxide intermediate is not the rat e-limiting step.