Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University , Guangzhou 510006, China.
Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
J Am Chem Soc. 2017 Feb 22;139(7):2766-2770. doi: 10.1021/jacs.6b12371. Epub 2017 Feb 1.
The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.
首次使用密度泛函理论（DFT）中的 M06-2X 函数研究了重氮化合物作为杂二烯亲体与二烯的 Diels-Alder（DA）反应的实验实例。为了进行比较，通过扭曲/相互作用模型分析了重氮酯作为亲二烯体或 1,3-偶极子与 1,3-二烯在分子间模型体系中的反应活性。1,3-偶极环加成对于分子间体系是非常有利的。而分子内的例子是独特的，因为连接基强烈有利于（4 + 2）环加成。
