Trapping Reactive Metal-Carbene Complexes by a Bis-Pocket Porphyrin: X-ray Crystal Structures of Ru=CHCO2Et and trans-[Ru(CHR)(CO)] Species and Highly Selective Carbenoid Transfer Reactions

被引：36

作者：

Deng, Qing-Hai ^{[1
]}

Chen, Jian ^{[1
]}

Huang, Jie-Sheng ^{[2
,3
]}

Chui, Stephen Sin-Yin ^{[2
,3
]}

Zhu, Nianyong ^{[2
,3
]}

Li, Guang-Yu ^{[1
]}

Che, Chi-Ming ^{[1
,2
,3
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, Shanghai 200032, Peoples R China

[2] Univ Hong Kong, Inst Mol Technol Drug Discovery & Synth, Dept Chem, Hong Kong, Hong Kong, Peoples R China

[3] Univ Hong Kong, Inst Mol Technol Drug Discovery & Synth, Open Lab Chem Biol, Hong Kong, Hong Kong, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2009年 / 15卷 / 41期

关键词：

carbenoids; porphyrinoids; reactive intermediates; ruthenium; structure elucidation; CHIRAL RUTHENIUM PORPHYRINS; C-H INSERTION; ETHYL DIAZOACETATE; ASYMMETRIC CYCLOPROPANATION; CATALYZED CYCLOPROPANATION; COPPER(I) CARBENES; ALLYLIC COMPOUNDS; ALKENES; MECHANISM; OLEFINS;

D O I：

10.1002/chem.200901895

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

What's in my pockets? By employing Suslick's bis-pocket porphyrin (ttppp), a reactive M=CHCO2Et complex and a trans-[M(CHR)(CO)] (M = Ru) complex have been structurally characterized by X-ray crystal analysis. The sterically encumbered ttppp ligand has a significant impact on both the diastereoselectivity and chemoselectivity in metalloporphyrin-catalyzed reactions of ethyl diazoacetate with conjugated aryl dienes. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：10707 / 10712

页数：6

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