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Geometrical Dependence of the Highest Occupied Molecular Orbital in Bicyclic Systems: π‐Facial Stereoselectivity of Bicyclic and Tricyclic Olefins
Author(s) -
Tsuji Motonori
Publication year - 2015
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201500054
Subject(s) - chemistry , electrophile , bicyclic molecule , stereoselectivity , steric effects , atomic orbital , selectivity , molecular orbital , electrophilic addition , computational chemistry , tricyclic , stereochemistry , molecule , organic chemistry , physics , quantum mechanics , catalysis , electron
Sterically unbiased bicyclic and tricyclic olefins were reacted with electrophiles to assess the π‐facial stereoselectivity. The stereochemical preference of the reactions of these olefins with electrophiles is attributed to the HOMO, which is derived from the interaction between a higher‐lying π orbital and particular lower‐lying σ orbitals. The selectivity of electrophilic reactions of these olefinic molecules is thought to be controlled by two types of HOMO, which are formed by a combination of different orbitals, depending on the geometrical conditions. A novel interpretation of orbital interactions enabled us to account for the facial selectivity in a unified manner.