Lewis acid-promoted α-hydroxy β-dicarbonyl to α-ketol ester rearrangement

• Type of Material: Article
• Authors: Xuechuan Hong, Emory University; Jose M. Mejia-Oneto, Emory University; Albert Padwa, Emory University
• Language: English
• Date: 2006-11-20
• Publisher: Elsevier
• Publication Version: Author Accepted Manuscript (After Peer Review)
• Copyright Statement: © 2006 Elsevier Ltd. All rights reserved.
• License: Creative Commons Attribution-NonCommercial-NoDerivs 2.5 Generic
• Final Published Version (URL): http://dx.doi.org/10.1016/j.tetlet.2006.09.071
• Title of Journal or Parent Work: Tetrahedron Letters
• ISSN: 0040-4039
• Volume: 47
• Issue: 47
• Start Page: 8387
• End Page: 8390
• Grant/Funding Information: We appreciate the financial support provided by the National Institutes of Health (GM 059384) and the National Science Foundation (CHE-0450779).
• Research Categories: Chemistry, General

Abstract

The decarbomethoxylation reaction of a substituted α-hydroxy-α-carbomethoxy pentacyclic substituted ketone, used as an advanced intermediate in the synthesis of the alkaloid aspidophytine, can be elected by heating with MgI2 in CH3CN. The reaction was shown to proceed by a novel α-hydroxy β-dicarbonyl to α-ketol ester rearrangement. It was possible to isolate a carbonate intermediate in 75% yield, thereby providing support for the proposed pathway.