Radicals masquerading as electrophiles: Dual orbital effects in nitrogen-philic acyl radical cyclization and related addition reactions

被引:128
|
作者
Schiesser, Carl H. [1 ]
Wille, Uta
Matsubara, Hiroshi
Ryu, Ilhyong
机构
[1] Univ Melbourne, Sch Chem, Melbourne, Vic 3010, Australia
[2] Univ Melbourne, Mol Sci & Biotechnol Inst Bio21, Melbourne, Vic 3010, Australia
[3] Osaka Prefecture Univ, Grad Sch Sci, Dept Chem, Sakai, Osaka 5998531, Japan
关键词
D O I
10.1021/ar600015v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Free-radical chemistry has come a long way in a relatively short period of time. The synthetic practitioner takes for granted the wealth of mechanistic and rate constant data now available and can apply free-radical techniques to the synthesis of many different classes of target molecule with confidence. Despite this, there are still mechanistic anomalies that need to be addressed. This Account highlights recent work involving nucleophilic radicals with low-lying unoccupied orbitals, such as acyl, oxyacyl, silyl, stannyl, and germyl radicals. Through interesting singly occupied molecular orbital (SOMO)-pi* and highest occupied molecular orbital (HO-MO)-lowest unoccupied molecular orbital (LUMO) interactions during these reactions, the radicals involved are able to mask as electrophiles, providing high levels of regiocontrol and efficient methods for the synthesis of important heterocycles.
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页码:303 / 313
页数:11
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