Ruthenium-assisted synthesis of gem-deuterated alkenes from monosubstituted propargyl alcohols and D2O

被引：12

作者：

Bianchini, C ^{[1
]}

de los Rios, I ^{[1
]}

Lopez, C ^{[1
]}

Peruzzini, M ^{[1
]}

Romerosa, A ^{[1
]}

机构：

[1] CNR, Ist Studio Stereochim & Energet Composti Coor, I-50132 Florence, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 593卷

关键词：

hydrolysis; vinylidenes; ruthenium; allyl compounds; reaction mechanisms;

D O I：

10.1016/S0022-328X(99)00324-1

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cyclohexenylvinylidene complex fac,cis-[(PNP)RuCl2{C=CH(C=CHCH2CH2CH2CH2)}] (2) is synthesized by reaction of mer, trans-[(PNP)RuCl2(PPh3)] (1) with 1-ethynylcyclohexanol [PNP=CH3CH2CH2N(CH2CH2PPh2)(2)]. Complex 2 reacts with water yielding fac,cis-[(PNP)RuCl2(CO)] and methylenecyclohexane. The regioselective incorporation of deuterium from D2O into the methylene group of methylenecyclohexane is consistent with the intermediacy of an eta(1)-allyl ruthenium complex along the metal-assisted hydrolysis of the vinylidene C-C bond. The hydrolysis of the alkenylvinylidenes fac,cis-[(PNP)RuCl2{C=CHCR=CH2}] (R = Me, Ph) proceeds similarly but the regioselectivity of deuterium incorporation depends on the temperature due to eta(1) double left right arrow eta(3) allyl interconversion. (C) 2000 Elsevier Science S.A. All rights reserved.

引用

页码：485 / 488

页数：4

共 16 条

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