Synthetic applications in radical/radical cationic cascade reactions

被引：29

作者：

Rinderhagen, H ^{[1
]}

Mattay, J ^{[1
]}

机构：

[1] Univ Bielefeld, Fak Chem, D-33501 Bielefeld, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2004年 / 10卷 / 04期

关键词：

domino reactions; electron transfer; polycycles; radical ions; radical reactions;

D O I：

10.1002/chem.200304827

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Oxidative photoinduced electron transfer (PET) reactions have been performed with various cyclic cyclopropyl(vinyl) silyl ethers bearing an olefinic or acetylenic side chain. The reactions result in bi- to tetracyclic ring systems via a fragmentation-radical/ radical cationic addition reaction pathway with well defined ring juncture. The mode of cyclisation (endo/exo) can be partially controlled by addition of nucleophiles due to the suppression of radical cationic reaction pathways. Quantum chemical calculation of the cyclisation transition states underline the experimentally found selectivities. Additional mechanistic studies concerning the saturation step reveal that the final radical is saturated mostly by the solvent and traces of water in the solvent.

引用

页码：851 / 874

页数：24

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