BETA-HYDRIDE ELIMINATION AND REGIOSELECTIVITY IN THE RHODIUM-CATALYZED HYDROFORMYLATION OF OPEN-CHAIN UNSATURATED ETHERS

被引：35

作者：

LAZZARONI, R ^{[1
]}

SETTAMBOLO, R ^{[1
]}

UCCELLOBARRETTA, G ^{[1
]}

机构：

[1] UNIV PISA,CNR,IST CHIM QUANTIST & ENERGET MOLEC,I-56126 PISA,ITALY

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 10期

关键词：

D O I：

10.1021/om00010a031

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The influence of the temperature on the regioselectivity in the rhodium-catalyzed hydroformylation of ethyl vinyl ether and ethyl allyl ether has been investigated in the range 20-120 degrees C. For both substrates, the amount of branched aldehyde decreases as the temperature increases, this effect being more pronounced for ethyl allyl ether than for ethyl vinyl ether. The H-2 NMR investigation of the deuterioformylation products obtained at partial conversion, with particular attention to the unconverted substrates, points out the different behavior of the metal. alkyl intermediates: at room temperature their formation is irreversible, at high temperature it becomes reversible for both isomers in the case of ethyl vinyl ether, but only for the branched one in the case of ethyl allyl ether. These results fully account for the observed influence of the temperature as well as the substrate structure on the regioselectivity.

引用

页码：4644 / 4650

页数：7

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