Catalytic Asymmetric Epoxidation Using a Fructose-Derived Catalyst
- Andy Burke ,
- Patrick Dillon ,
- Kyle Martin , and
- T. W. Hanks
Abstract
Modern epoxidation methods are able to create two adjacent stereocenters with very high enantioselectivity. Opening of the epoxides with nucleophiles permits rapid entry into complex organic systems, making this powerful synthetic methodology one of the fundamental reactions in organic synthesis. Various reagents for generating epoxides have been developed, including the dioxiranes. These oxidants are typically generated in situ from a ketone. Recently, a chiral dioxirane has been prepared from fructose and shown to catalytically deliver an oxygen from a simple, symmetrical oxidant to a wide variety of alkenes in very high yields and with excellent selectivity. This reaction makes an effective experiment for advanced undergraduates. Both the synthesis of the catalyst and the epoxide product are easily purified and lend themselves well to analysis by the standard array of techniques available to the organic chemist. Enantioselectivity can be determined either by polarimetry or by NMR shift experiments. In addition, the mechanism of the asymmetric epoxidation can be explored by a combination of computer modeling and student-proposed research experiments.
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This article is cited by 6 publications.
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- Kendrew K. W. Mak , Y. M. Lai , and Yuk-Hong Siu . Regiospecific Epoxidation of Carvone: A Discovery-Oriented Experiment for Understanding the Selectivity and Mechanism of Epoxidation Reactions. Journal of Chemical Education 2006, 83 (7) , 1058. https://doi.org/10.1021/ed083p1058
- Bernard Bessières and, Christophe Morin. Iodomethyl Group as a Hydroxymethyl Synthetic Equivalent: Application to the Syntheses of d-manno-Hept-2-ulose and l-Fructose Derivatives. The Journal of Organic Chemistry 2003, 68 (10) , 4100-4103. https://doi.org/10.1021/jo0342166
- Waldemar Adam, Chantu R. Saha-Möller, Cong-Gui Zhao. Dioxirane Epoxidation of Alkenes. 2014,,, 1-309. https://doi.org/10.1002/9780470466759.ch1
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