Ketone-Imide versus Ketone-Oxime Reductive Cross-Coupling Promoted by Samarium Diiodide:  New Mechanistic Insight Gained from a Failed Aminocyclopentitol Synthesis

Jose Luis Chiara,* Ángela García, and Gabriella Cristóbal-Lumbroso
Instituto de Qumica Orgnica General, CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain
J. Org. Chem., 2005, 70 (10), pp 4142–4151
DOI: 10.1021/jo050185y
Publication Date (Web): April 12, 2005
Copyright © 2005 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, jl.chiara@iqog.csic.es

Abstract

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The intramolecular 1,6-ketone/imide reductive coupling promoted by samarium diiodide competes favorably with an alternative 1,5-ketone/oxime ether coupling in a keto-oxime substrate derived from d-glucosamine N-protected with a phthalimido group. This pinacol coupling reaction affords new homochiral α-hydroxylactam scaffolds that could be useful in diversity-oriented synthesis. A mechanistic proposal for this reaction that explains the experimental results is supported by DFT quantum-mechanical calculations on model compounds.

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History

  • Published In Issue May 13, 2005
  • Received January 28, 2005

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