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. Issue 3 (23rd January 2015)

• Record Type: Journal Article
• Authors: Huang, Pingping; Liu, Lingyan; Chang, Weixing; Li, Jing
• Is Part Of: Chemistry, an Asian journal. Volume 10:Issue 3(2015:Mar.)
• Page Start: 548
• Page End: 552
• Publication Date: 2015-01-23
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201403092
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>An unexpected double Diels–Alder (DDA) reaction of (<italic>E</italic>)‐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.</p> </abstract>