HOMOGENEOUS CATALYSIS - CATALYTIC INTRAMOLECULAR CONVERSION OF 1,4-DIALDEHYDES TO GAMMA-LACTONES

被引:71
作者
BERGENS, SH [1 ]
FAIRLIE, DP [1 ]
BOSNICH, B [1 ]
机构
[1] UNIV TORONTO,LASH MILLER CHEM LABS,TORONTO M5S 1A1,ONTARIO,CANADA
关键词
D O I
10.1021/om00117a006
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of catalysts of the type [Rh(diphosphine)(solvent)2]+ (solvent = weakly coordinating solvent) were investigated for converting 1,4-dialdehydes and 1,4-keto aldehydes to the corresponding γ-lactones, the equivalent of the intramolecular Cannizzaro reaction. It was found that a number of these species were very effective catalysts which tolerated a high degree of steric hindrance and transformed the substrates without any detectable enolization. The carbonylated species [Rh(diphosphine)(CO)2]+ and [Rh(diphosphine) (CO) (solvent)]+ are ineffective in catalysis and are the side products of intramolecular lactonization. Decarbonylation of the substrate to give these inactive carbonylated species is a minor component of the catalysis with 1,4-dialdehydes but is the major pathway for the lactonization of 1,4-ketoaldehydes. These catalysts provide a practical, mild catalytic method of converting 1,4-dialdehydes to 7-lactones. The catalysis is very rapid, occurring even at −60 °C. At −78 °C a stable substrate (η2-aldehyde)rhodium adduct was identified and is possibly the precursor to aldehyde C–H activation. No other catalytic intermediates could be intercepted at low temperatures. The catalysis appears to be a “black box” system where, once the C–H bond is activated, none of the putative intermediates exist in detectable concentrations. © 1990, American Chemical Society. All rights reserved.
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页码:566 / 571
页数:6
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