Copper-Catalyzed Alkene Aminoazidation as a Rapid Entry to 1,2-Diamines and Installation of an Azide Reporter onto Azahetereocycles.

Published

Journal Article

A copper-catalyzed aminoazidation of unactivated alkenes is achieved for the synthesis of versatile unsymmetrical 1,2-diamine derivatives. This transformation offers an effective approach to installing an amide and an azide from two diffenent amino precursors onto both terminal and internal alkenes, with remarkable regio- and stereoselectivity. Mechanistic studies show that this diamination reaction proceeds via a nucleophilic amino cyclization followed by an intermolecular C-N bond formation using electrophilic azidoiodinane. This pathway differs from previous azidoiodinane-initiated alkene functionalization, suggesting new reactivity of azidoiodinane. Furthermore, this aminoazidation reaction provides an efficient strategy to introduce azide, one of the most useful chemical reporters, onto a broad range of bioactive azaheterocycles, offering new opportunities in bioorthogonal chemistry and biological studies. Rapid syntheses of 5-HT2C agonist, (-)-enduracididine and azido-cholesterol derivatives demonstrate broad applications of this method in organic synthesis, medicinal chemistry, and chemical biology.

Full Text

Duke Authors

Cited Authors

  • Shen, K; Wang, Q

Published Date

  • September 5, 2017

Published In

Volume / Issue

  • 139 / 37

Start / End Page

  • 13110 - 13116

PubMed ID

  • 28825822

Pubmed Central ID

  • 28825822

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.7b06852

Language

  • eng