RH(II)-CATALYZED ISOMERIZATIONS OF CYCLOPROPENES - EVIDENCE FOR RH(II)-COMPLEXED VINYLCARBENE INTERMEDIATES

被引：72

作者：

MULLER, P ^{[1
]}

PAUTEX, N ^{[1
]}

DOYLE, MP ^{[1
]}

BAGHERI, V ^{[1
]}

机构：

[1] TRINITY UNIV, DEPT CHEM, SAN ANTONIO, TX 78212 USA

来源：

HELVETICA CHIMICA ACTA | 1990年 / 73卷 / 05期

关键词：

D O I：

10.1002/hlca.19900730513

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The thermocatalytic rearrangements of cyclopropenes 1‐4 have been investigated in the presence of Rh(IT) perfiuorobutyrate. 1, 2, 3‐Triphenylcyclopropene (1a) undergoes rearrangement lo diphenylindene 5a or, with alkoxycyclopropene derivatives, to α, β‐unsaturated ketone 6. Furan formation occurs with 2, 3‐diphenylcyclo‐propenecarboxylate 2, but the diethyl counterpart 3 rearranges to dienoate 8. 2‐Alkylcyclopropenecarboxylates 4 afforded (E)‐methylidenecyclopentane derivatives 9 as the only isolable product in yields of ca. 35 %. A mechanism involving regio‐ and stereospecific cyclopropene ring opening to a Rh‐complexed vinylcarbene and insertion of the latter into the CH bond to give 9 is proposed. An analogous mechanism should account for the rearrangement products of 1 to 3. Copyright © 1990 Verlag GmbH & Co. KGaA, Weinheim

引用

页码：1233 / 1241

页数：9

共 51 条

[1] THE STEREOSELECTIVITY OF RING-OPENING OF 3-SUBSTITUTED CYCLOPROPENES AND INTERMOLECULAR TRAPPING OF DERIVED VINYLCARBENES [J].