Journal article
Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates
Journal of organic chemistry, Vol.59(26), pp.8197-8202
12/01/1994
DOI: 10.1021/jo00105a042
Abstract
A series of chiral auxiliaries has been tested for viability in the vinyl phosphate/β-keto phosphonate rearrangement. While dienyl phosphates derived from ephedrine, pseudoephedrine, and isopinocampheol succumbed to competing elimination reactions, ones derived from menthol and (S)-2-methylbutanol were found to undergo rearrangement to the desired β-keto phosphonates. The bis((S)-2-methylbutyl) phosphorochloridate then was used to prepare the vinyl phosphates of the prochiral ketone 4-methylcyclohexanone, and modest diastereoselectivity was observed upon rearrangement of these phosphates to the corresponding β-keto phosphonates. The de of this rearrangement was established by degradation of the β-keto phosphonate to 3-methyladipic acid and determination of the optical rotation. This sequence allowed identification of the major rearrangement product as the 4R-diastereomer of β-keto phosphonate 13. Finally, two other prochiral cyclohexanones were found to be suitable substrates for the vinyl phosphate/β-keto phosphonate rearrangement. © 1994, American Chemical Society. All rights reserved.
Details
- Title: Subtitle
- Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates
- Creators
- Yi-Zhong AnJian Guo AnDavid F Wiemer
- Resource Type
- Journal article
- Publication Details
- Journal of organic chemistry, Vol.59(26), pp.8197-8202
- Publisher
- American Chemical Society
- DOI
- 10.1021/jo00105a042
- ISSN
- 0022-3263
- eISSN
- 1520-6904
- Language
- English
- Date published
- 12/01/1994
- Academic Unit
- Neuroscience and Pharmacology; Chemistry
- Record Identifier
- 9984216700202771
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