Journal article
Diastereoselective Vinyl Phosphate/β-Keto Phosphonate Rearrangements
Journal of organic chemistry, Vol.61(12), pp.4040-4045
01/01/1996
DOI: 10.1021/jo9518157
PMID: 11667280
Abstract
Several nonracemic diols and amino alcohols have been tested for their utility as chiral auxiliaries in vinyl phosphate/β-keto phosphonate rearrangements. When (2R,4R)- or (2S,4S)-pentane-2,4-diol were employed, the diastereomeric β-keto phosphonates obtained from three prochiral cyclohexanones gave separate resonances in their respective 31P NMR spectra, allowing estimation of diastereomeric excess (de) via straightforward integration. A crystalline enol form of the β-keto phosphonate was obtained from one ketone (4-(1,1-(ethylenedioxy)ethyl)-4-methylcyclohexanone, 10), which allowed determination of its absolute stereochemistry by X-ray diffraction analysis. When LTMP was used to induce rearrangement of vinyl phosphates derived from ketone 10 and (2R,4R)-or (2S,4S)-pentane-2,4-diol, a de of 2.5:1 was obtained. In addition, de values of 2.0:1 and 1.4:1 were obtained with parallel rearrangements of 4-isopropyl- and 4-methylcyclohexanone, suggesting that this sequence may be more generally applicable to preparation of nonracemic materials from prochiral cyclohexanones.
Details
- Title: Subtitle
- Diastereoselective Vinyl Phosphate/β-Keto Phosphonate Rearrangements
- Creators
- Jianguo An - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242-1294Jeffrey M Wilson - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242-1294Yi-Zhong An - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242-1294David F Wiemer - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242-1294
- Resource Type
- Journal article
- Publication Details
- Journal of organic chemistry, Vol.61(12), pp.4040-4045
- DOI
- 10.1021/jo9518157
- PMID
- 11667280
- NLM abbreviation
- J Org Chem
- ISSN
- 0022-3263
- eISSN
- 1520-6904
- Language
- English
- Date published
- 01/01/1996
- Academic Unit
- Neuroscience and Pharmacology; Chemistry
- Record Identifier
- 9984216667502771
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