RADICAL-ADDITION TO ALKENES VIA ELECTRON-TRANSFER PHOTOSENSITIZATION

被引:30
作者
FAGNONI, M [1 ]
MELLA, M [1 ]
ALBINI, A [1 ]
机构
[1] UNIV PAVIA, DIPARTIMENTO CHIM ORGAN, I-27100 PAVIA, ITALY
关键词
D O I
10.1021/ja00135a004
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A method for radical addition to alkenes is reported which is based on the photosensitized oxidation of a tetraalkylstannane by an excited acceptor (A*), fragmentation of the radical cation, and addition of the thus formed radical to an electron-withdrawing substituted alkene (acrylonitrile and dimethyl maleate). Aromatic nitriles and esters can be used as the electron accepters, and they are chosen in such a way that their radical anion (A(.-)) reduces the adduct (and not the educt) radical. In this way the adduct radical is reduced and protonated to yield the end product, and the acceptor functions as a nonconsumed electron transfer sensitizer. In several cases the alkylation occurs more efficiently in the presence of a secondary donor (phenanthrene or biphenyl). However, when the acceptor is too easily reduced in the ground state (as with 1,2,4,5-benzenetetracarbonitrile), coupling of the adduct radical with A(.-) competes with its reduction.
引用
收藏
页码:7877 / 7881
页数:5
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