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An Unexpected Double Diels–Alder Reaction of ( E )‐2‐Bromo‐4‐aryl‐1,3‐pentadiene Involving [1,5]‐Hydrogen Migration and HBr Elimination: Synthesis of Bicyclo[2.2.2]octene Derivatives
Author(s) -
Huang Pingping,
Liu Lingyan,
Chang Weixing,
Li Jing
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201403092
Subject(s) - steric effects , diene , chemistry , synthon , aryl , bicyclic molecule , catalysis , medicinal chemistry , diels–alder reaction , stereochemistry , organic chemistry , alkyl , natural rubber
An unexpected double Diels–Alder (DDA) reaction of ( E )‐2‐bromo‐4‐aryl‐1,3‐pentadiene was developed and resulted in a series of “butterfly‐like” bicyclo[2.2.2]octene derivatives in moderate to good yields without the need for a metal catalyst. The proposed mechanism involves a [1,5]‐sigmatropic hydrogen migration and HBr elimination. Through this decisive [1,5]‐hydrogen shift step, the electronic properties and steric hindrance of the conjugated diene substrate are completely altered and the DDA reaction of this potential diene synthon is successfully achieved.