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
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