Origins of regioselectivity in 1,3-dipolar cycloadditions of nitrile oxides with alkynylboronates

被引：15
|
作者：
Lin, Bernice [1 ]
Yu, Peiyuan [1 ]
He, Cyndi Qixin [1 ]
Houk, K. N. [1 ]
机构：
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
来源：
BIOORGANIC & MEDICINAL CHEMISTRY | 2016年 / 24卷 / 20期
基金：
美国国家科学基金会;
关键词：
DFT; Cycloadditions; Distortion/interaction model; Isoxazoles; Regioselectivity; MOLECULAR-ORBITAL THEORY; DENSITY FUNCTIONALS; REACTIVITY; DISTORTION/INTERACTION;
D O I：
10.1016/j.bmc.2016.07.032
中图分类号：
Q5 [生物化学]; Q7 [分子生物学];
学科分类号：
071010 ; 081704 ;
摘要：
Density functional theory (M06-2X) studies of the regioselectivity of 1,3-dipolar cycloaddition reactions of benzo and mesitonitrile oxides with alkynyl pinacol and MIDA boronates are reported. Calculated relative free energies of activation reproduce the experimentally observed product ratios. The electronic energies of activation are found to be mainly controlled by distortion energies required to achieve the transition states. Both electronic and steric effects influence regioselectivities. (C) 2016 Elsevier Ltd. All rights reserved.
引用
收藏
页码：4787 / 4790
页数：4
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