什么控制了麦农酮与硝代苯乙烯的 1,3-偶极环加成反应的区域化学？
What controls regiochemistry in 1,3-dipolar cycloadditions of münchnones with nitrostyrenes?
机构信息
Department of Chemistry, Dartmouth College , Hanover, New Hampshire 03755, United States.
出版信息
Org Lett. 2013 Oct 18;15(20):5218-21. doi: 10.1021/ol402385v. Epub 2013 Sep 27.
PMID:24073889
Abstract
The distinct experimentally observed regiochemistries of the reactions between mesoionic münchnones and β-nitrostyrenes or phenylacetylene are shown by DFT/BDA/ETS-NOCV analyses of the transition states to be dominated by steric and reactant reorganization factors, rather than the orbital overlap considerations predicted by Frontier Molecular Orbital (FMO) Theory.
摘要
通过对过渡态的密度泛函理论（DFT）/双原子轨道理论（BDA）/扩展过渡态理论（ETS-NOCV）分析表明，中氮茂甲酮与β-硝基苯乙烯或苯乙炔之间的反应在实验上观察到的区域化学性质明显受空间位阻和反应物重排因素的支配，而不是由前沿分子轨道（FMO）理论预测的轨道重叠考虑因素所决定。
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