Journal article
Regiospecific Vinyl Phosphate/β-Keto Phosphonate Rearrangements Initiated by Halogen−Metal Exchange
Journal of organic chemistry, Vol.63(8), pp.2613-2618
04/01/1998
DOI: 10.1021/jo972131x
PMID: 11672127
Abstract
A new strategy has been developed for preparation of β-keto phosphonates via a halogen-metal exchange induced 1,3-phosphorus migration of 2-bromovinyl phosphates. These intermediates can be prepared through conversion of an α-bromo ketone to the appropriate enolate by reaction with strong base, or through conjugate addition to an α-bromo α,β-unsaturated ketone. In either case, trapping the resulting enolate by reaction with a dialkyl phosphorochloridate gives the 2-bromovinyl phosphate. Metalation can be accomplished upon treatment with n-BuLi, and rearrangement is facile once metalation has been achieved. Studies with isotopically labeled substrates have shown that this rearrangement is regiospecific, in contrast to vinyl phosphate/β-keto phosphonate rearrangements induced by strong base where regioisomeric products are sometimes obtained.
Details
- Title: Subtitle
- Regiospecific Vinyl Phosphate/β-Keto Phosphonate Rearrangements Initiated by Halogen−Metal Exchange
- Creators
- Tracy J Baker - 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.63(8), pp.2613-2618
- DOI
- 10.1021/jo972131x
- PMID
- 11672127
- NLM abbreviation
- J Org Chem
- ISSN
- 0022-3263
- eISSN
- 1520-6904
- Language
- English
- Date published
- 04/01/1998
- Academic Unit
- Neuroscience and Pharmacology; Chemistry
- Record Identifier
- 9984217456802771
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