University Chemistry ›› 2017, Vol. 32 ›› Issue (8): 60-65.doi: 10.3866/PKU.DXHX201701017

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A DFT Study on the Rearrangement of Carbanion

Wen-Feng WANG*(),Yao-Feng YUAN,Jun-Qian LI   

  • Published:2017-08-15
  • Contact: Wen-Feng WANG E-mail:wangwf@fzu.edu.cn
  • Supported by:
    福建省自然科学基金(2017J01578);福州大学高等教育教学改革工程项目

Abstract:

The molecular orbitals of transition states of 1, 2-shift and 1, 4-shift of carbanion were calculated using the density functional theory (DFT) method. It was found that the migration atom carried positive charge and the rest of the carbanion became a double carbanion. In the transition state of 1, 2-shift, the phase of HOMO of the double carbanion doesn't match that of LUMO of the migration atom. However, in the transition state of 1, 4-shift, the phase of HOMO of the double carbanion matches that of LUMO of the migration atom. So the 1, 2-shift of carbanion is an orbital symmetry prohibited reaction and the 1, 4-shift of carbanion is an orbital symmetry permitted reaction. The calculation in this paper can afford a valuable reference for the teaching of advanced organic chemistry.

Key words: Carbanion, Rearrangement, Orbital symmetry, Chemical calculation

MSC2000: 

  • G64