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DOI: 10.1055/s-0029-1217352
Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins
Publication History
Received
19 December 2008
Publication Date:
12 June 2009 (online)
Abstract
Biomimetic and other strategies that have been developed in the author’s laboratory for the synthesis of a subset of the group of enzymically oxidized lipids known as oxylipins are described. This set of oxylipins contains both a cyclopropane and a lactone, with the lactone ring size varying between six and nine members. A biomimetic approach employing cascade cyclization of an epoxyalkenoic acid was successful in creating the cyclopropane and six-membered lactone of C20 oxylipins such as the constanolactones in a single step, but failed in an attempt to create the nine-membered lactone of halicholactone. Solandelactones, C22 oxylipins containing a cyclopropane and an eight-membered lactone, were synthesized by directed Simmons-Smith cyclopropanation followed by Claisen rearrangement of a cyclic ketene acetal to construct the lactone
1 Introduction
2 The First Biomimetic Cascade Synthesis of an Oxylipin
3 Biomimetic Cascade Synthesis of Constanolactones A and B
4 A Failed Biomimetic Strategy for Halicholactone
5 Synthesis of the C22 Oxylipins Solandelactones A, B, E, and F
5.1 A Ring-Closing Metathesis Approach to the Octenalactone Portion of Solandelactones
5.2 The Petasis-Claisen Rearrangement Route to the Octenalactone Portion of Solandelactones
6 Conclusion
Key words
biomimetic synthesis - cascade synthesis - cyclopropanation - Claisen rearrangement - lactones - lipids