ORGANIC SYNTHESES VIA TRANSITION-METAL COMPLEXES .51. 1-METALLA-1,3,5-TRIENES AND 1-METALLA-1,3-DIEN-5-YNES OF CHROMIUM AND TUNGSTEN BY INSERTION OF ALKYNES INTO M=C AND C=C BONDS OF 1-METALLA-1,3-DIENES AND 1-METALLA-1-EN-3-YNES, RESPECTIVELY

被引：53

作者：

AUMANN, R ^{[1
]}

HEINEN, H ^{[1
]}

HINTERDING, P ^{[1
]}

STRATER, N ^{[1
]}

KREBS, B ^{[1
]}

机构：

[1] UNIV MUNSTER,INST ANORGAN CHEM,W-4400 MUNSTER,GERMANY

来源：

CHEMISCHE BERICHTE | 1991年 / 124卷 / 05期

关键词：

CARBENE COMPLEXES OF CHROMIUM AND TUNGSTEN; 1-METALLA-1,3,5-TRIENES; 1-METALLA-1,3-DIEN-5-YNES; INSERTION OF ALKYNES INTO M=C AND C=C BONDS; 2+2] CYCLOADDITION REACTIONS OF CARBENE COMPLEXES AND ALKYNES;

D O I：

10.1002/cber.19911240541

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

1-Metalla-1,3,5-trienes L(n)M = C(NEt2) - C(Me) = C(OEt) - CH = CHPh (3, 4) and L(n)M = C(OEt) - CH = C(NEt2) - C(Me) = CHPh [5, L(n)M = Cr(CO)5 (a), W(CO)5 (b)] are obtained for the first time from the corresponding 1-metalla-1,3-dienes L(n)M = C(OEt) - CH = CHPh (1a, b) under very mild conditions by the insertion of the electron-rich alkyne Et2N - C = C - Me (2) into the M = C and the C = C bonds, respectively, of 1. The chelate complex L(n-1) Activated W = C(OEt) - CH = C(NEt2) - C(Me) = CHPh (6b) and the cyclobutenyl carbene complex 7b are isolated as minor side products. 1-Metalla-1,3-dien-5-ynes L(n)M = C(NEt2) - C(Me) = C(OEt) - C = CPh [9, 10, L(n)M = Cr(CO)5 (a), W(CO)5 (b)] are formed with high regio- and stereoselectivity on insertion of 2 into the M = C bonds of 1-metalla-1-en-3-ynes 8. X-ray data are given for the tungsten complex 3b.

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页码：1229 / 1236

页数：8

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