Construction of six-membered nitrogen-heterocycles via intramolecular cyclization of iminyl radical: A theoretical perspective

被引：4

作者：

Chi, Yu-juan ^{[1
]}

Yu, Hai-tao ^{[1
]}

机构：

[1] Heilongjiang Univ, Sch Chem & Mat Sci, Key Lab Funct Inorgan Mat Chem, Minist Educ, Harbin 150080, Peoples R China

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2013年 / 1025卷

基金：

中国国家自然科学基金;

关键词：

Radical cyclization; Regioselectivity; 4-Penteniminyl radical; Intrinsic reaction barrier; Six-membered N-heterocycle; GAUSSIAN-BASIS SETS; GAS-PHASE SYNTHESIS; DENSITY-FUNCTIONAL THERMOCHEMISTRY; CORRELATED MOLECULAR CALCULATIONS; EFFECTIVE CORE POTENTIALS; RING-CLOSURE; AB-INITIO; ELECTRON-TRANSFER; CHAIN REACTIONS; RATE CONSTANTS;

D O I：

10.1016/j.comptc.2013.10.009

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

In this study, we reported a potential method of constructing six-membered nitrogen-containing heterocycles via intramolecular cyclization of R-2-substituted 4-penteniminyl radicals (R-2 = -NO2, -SO2OH, -CF3, -SO2Ph, -CN, -CONMe2, -p-PhNO2, and -COOH). All of these investigated iminyl radicals exhibit strong preference for 6-endo cyclization products over 5-exo products. We further explored possible reasons to lead to the predominant 6-endo regioselectivity, including electronic density, stereoelectronic effect (intrinsic barrier), and thermodynamic contribution to reaction barrier. The computed results provided a potential synthetic strategy towards constructing six-membered N-heterocycles by intramolecular cyclization of substituted iminyl radicals. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：52 / 57

页数：6

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