Ketone-imide versus ketone-oxime reductive cross-coupling promoted by samarium diiodide: new mechanistic insight gained from a failed aminocyclopentitol synthesis.

Jose Luis Chiara, Angela García, Gabriella Cristóbal-Lumbroso

Journal: The Journal of organic chemistry 2005;70(10):4142-51

PMID: 15876107

Abstract

[reaction: see text] 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 alpha-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.

Address: Instituto de Química Orgánica General, CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain. [email protected]

DOI: 10.1021/jo050185y

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MeSH Terms: Cyclization, Glucosamine, Glucosidases, Imides, Iodides, Ketones, Oximes, Samarium, Stereoisomerism