Cyclization of Imides to 2-Azabicycles via Aminoketyl Radicals by Using Samarium(II) Iodide-Water: Reaction Development, Synthetic Scope, and Mechanistic Studies

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Abstract

The first highly selective method for direct addition of aminoketyl radicals [R-C(O-)NR1R2], generated from five- or six-membered cyclic imides, to nonactivated π-systems by using the SmI2-H2O reagent is reported. The transformation is operationally simple, scalable, and provides access to valuable angular 2-azabicycles containing three contiguous stereocenters with excellent diastereoselectivity (>95:5 dr). The protocol accommodates a wide range of π-acceptors that can be modulated by the alcohol additive used. Notably, the transformation provides the first general method for generation of aminoketyl radicals by a direct electron capture to amide bonds, thus opening new vistas for applications of these underutilized intermediates in a diverse array of open-shell reaction pathways. Systematic studies on the effects of additives, the scope and limitations of the reaction, and the reaction mechanism are reported.

Original languageEnglish (US)
Article numberss-2016-c0066-st
Pages (from-to)1825-1854
Number of pages30
JournalSynthesis (Germany)
Volume48
Issue number12
DOIs
StatePublished - Jun 16 2016

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Keywords

  • aminoketyl radicals
  • azabicycles
  • cyclizations
  • reductive coupling
  • samarium diiodide
  • stereoselectivity
  • umpolung

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