References/Citations

References/Citations

Jung, M. E.; Lee, C. P. Org. Lett. 2001, 3, 333.

This paper shows a mechanism (see Figure 1 above) that is similar to the transformation from 7 to 8 in the previous paper. However this reaction, shows, a hydrogen rearrangement, not a carbocation rearrangement. Still, the fundamentals are the same. The oxygen that is not involved is protected with the TMS protecting group. The oxygen in the epoxide ring is then also protected by TMS. This causes the oxygen to have a positive charge which in turn causes the epoxide ring to open. The bond at the more substituted carbon breaks, because it can take the positive charge and still be more stable, and the epoxide ring breaks to give oxygen a neutral charge. The Hₐ can then move to fill the octet on the carbon and restore a neutral charge, and the other oxygen can donate an electron pair to form a double bond to take the place of the hydrogen. In the reaction from 7 to 8, the HC=CH₂ moves instead of a hydrogen, and the rest of the reaction involves deprotection.

Articles citing the above article:

1) Jung, M. E.; van den Heuvel, A. Tetrahedron Lett. 2002, 43, 8169-8172.
This paper expands on the properties of epoxide rearrangements by analyzing the mechanisms and results of diastereomers of silyloxy epoxides undergoing rearrangement.

2) Ehrlich, G.; Hassfeld, J.; Eggert, U.; Kalesse, M. J. Am. Chem. Soc. 2006, 43, 14038-14039.
This paper alludes to the above paper because of its work in synthesizing tedanolides.

3) Wang, H.; Houk, K. N.; Allen, D. A.; Jung, M. E.; Org. Lett. 2011, 13, 3238-3241.
This paper uses the processes involved in Lewis acid induced rearrangements to cause a 1,2 hydride shift in order to synthesize polyketide natural products.