Pt(Ⅱ)催化炔基氮丙啶合成环戊烷吡咯机理的密度泛函理论研究  

DFT study on the Pt~Ⅱ-catalyzed tetrahydrocyclopenta[b]pyrroles synthesis from 2-alkynyl-1-azaspiro[2. 3]hexanes

作　　者：张金生[1] 余晓娟[1] 

机构地区：[1]贵州师范大学化学与材料科学学院,贵州贵阳550001

出　　处：《贵州师范大学学报（自然科学版）》2016年第1期55-60,共6页Journal of Guizhou Normal University：Natural Sciences

基　　金：国家自然科学基金(No.21163003)

摘　　要：用量子化学密度泛函理论B3LYP方法在6-311G(d,p)的计算水平上对Pt Cl2催化2-炔基-1-氮杂环己烷合成1,4,5,6-四氢化环戊烷吡咯的反应,进行了计算,找到两条主要的反应通道,最优势反应路径包括炔基的活化、氮丙啶的氮与炔基间的环化反应、环异构化、质子转移和催化剂解离5个步骤。Pt Cl_2催化作用的本质在于Pt^(2+)与炔基配位,能降低炔基反键轨道π*_(C1-C2)的能级,降低炔基反键轨道π*_(C1-C2)与氮丙啶的氮原子孤电子占据轨道LP-(2p)_N的能级差,使丙啶氮原子与炔基之间的环化反应势垒下降。By means of density functional theory（ DFT）,the Pt~Ⅱ-Catalyzed mechanism for 1-benzyl-1,4,5,6-tetrahydrocyclopenta[b]pyrrole synthesis from 1-benzyl-2-ethynyl-1-azaspiro[2. 3]hexane was investigated. Two reaction channels were found. The overall reaction in the favored channel includes the activation of alkynyl,cyclization reaction,isomerization reaction,proton migration and regeneration of the catalyst. The substrate 1 was activated by its combination of Pt（ Ⅱ） to triple bond which leads to a decrease in the orbital energy of π＊_（ C1- C2）and the orbital energy-gap between π＊_（ C1- C2）and LP-（ 2p）_N.

关 键 词：炔基氮丙啶 四氢化环戊烷吡咯 环化反应 σ-π配键 密度泛函理论 

分 类 号：O641-3[理学—物理化学]