School of Chemical Sciences, Devi Ahilya University, Takshashila Campus, Indore, MP 452 001, India.
J Phys Chem A. 2010 Jan 21;114(2):1032-8. doi: 10.1021/jp9088222.
Present communication elicits an interesting interaction between 2H-azirine and a number of electron rich and electron deficient dienes. A series of substituted 2H-azirine 1-10, and three dienes namely cyclopentadiene D-1, furfural D-2, and dinitrofuran D-3 were chosen to investigate and critically review the reactivity and selectivity of Diels-Alder cycloaddition strategy. The global and local electrophilicity patterns have been evaluated to interpret the electrophilic/nucleophilic behavior of dienes D-1 to D-3 and dienophiles 1-10, in polar Diels-Alder cycloaddition, using the DFT method at the B3LYP/6-31G* level of theory. Regional nucleophilicity have been evaluated using local nucleophilicity descriptor N(k) (Perez, P.; Domingo, L. R.; Duque-Norena, M.; Chamorro, E. J. Mol. Struct. THEOCHEM 2009, 895, 86-91), and regional electrophilicity at the active sites of the interactive species involved in Diels-Alder processes have been described on a quantitative basis using local electrophilicity index omega(k).
本通讯引出了 2H-氮丙啶与许多富电子和缺电子二烯之间的有趣相互作用。选择了一系列取代的 2H-氮丙啶 1-10 和三种二烯，即环戊二烯 D-1、糠醛 D-2 和二硝基呋喃 D-3，以研究和批判性地审查 Diels-Alder 环加成策略的反应性和选择性。使用 DFT 方法在 B3LYP/6-31G*理论水平上评估了全局和局部电导率模式，以解释二烯 D-1 至 D-3 和双烯试剂 1-10 在极性 Diels-Alder 环加成中的亲电/亲核行为。使用局部亲核性描述符 N(k)（Perez，P.；Domingo，L. R.；Duque-Norena，M.；Chamorro，E. J. Mol. Struct. THEOCHEM 2009, 895, 86-91）评估了区域亲核性，并使用局部电导率指数 omega(k) 定量描述了 Diels-Alder 过程中涉及的交互物种的活性部位的区域电导率。
