Polyethers

• Published in: From Biosynthesis to Total Synthesis pp. 162 - 185
• Main Authors: Xie, Youwei, Floreancig, Paul E
• Format: Book Chapter
• Language: English
• Published: Hoboken, NJ John Wiley & Sons, Inc 22.04.2016
• Subjects: biosynthesis; cyclic ethers; enantioselective epoxidation methods; epoxide cascade reactions; intramolecular ring‐opening reactions; polyethers; regiocontrol; stereoselective epoxide synthesis
• ISBN: 1118751736; 9781118751732
• DOI: 10.1002/9781118754085.ch4

Numerous attributes make epoxides impressively versatile functional groups in chemical synthesis. Ring strain of approximately 24 kcal/mol is present in these structures, making them considerably more prone toward reactions with nucleophiles than unstrained ethers. This chapter describes the use of epoxides as biosynthetic precursors for cyclic ethers. The advances that allow for predictable chemical synthesis based on epoxide opening, including the development of models for regiocontrol in intramolecular ring‐opening reactions and stereoselective synthesis, are described. Advances in applying these studies to stereoselective oxacycle synthesis have been critically dependent upon the development of enantioselective epoxidation methods. Challenges still remain in this area despite the dramatic advances. The chapter ends with numerous examples of epoxide cascade reactions in natural product synthesis. Syntheses that utilize cascade reactions for the constructions of multiple rings of different size will certainly improve access to more complex ladder ethers.