FACILE SYNTHESIS OF ALPHA,BETA-UNSATURATED NIOBIUM ACYLS VIA GAMMA-HYDRIDE ABSTRACTION

被引：9

作者：

HNEIHEN, AS ^{[1
]}

FERMIN, MC ^{[1
]}

MAAS, JJ ^{[1
]}

BRUNO, JW ^{[1
]}

机构：

[1] WESLEYAN UNIV,HALL ATWATER LABS,MIDDLETOWN,CT 06459

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1992年 / 429卷 / 03期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/0022-328X(92)83191-J

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The niobocene ketene complexes [C5H4(SiMe3)]2Nb(Cl)(eta-2-C,O-O=C=C(R)CH2R') (1) undergo a facile reaction with Ph3C+BF4- to give the cationic alpha,beta-unsaturated metal acyls of general formula [[C5H4(SiMe3)]2Nb(Cl)(eta-2-C(O)CR=CHR')][BF4]. The reaction is stereospecific for the production of E-alkenes, but these undergo slow isomerization to a mixture of E and Z isomers. If both ketene substituents contain accessible allylic hydrogens, the reaction shows little regioselectivity. Preliminary mechanistic studies are consistent with a direct hydride abstraction rather than an electron-transfer/H atom transfer sequence.

引用

页码：C33 / C37

页数：5

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