Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions

Scott E Denmark, Chien Tien Chen

Research output: Contribution to journalArticle

Abstract

A general method for the preparation of enantiomerically enriched phosphonic acids and phosphonates with three different α-substitution patterns (aryl, alkyl, and alkoxy) has been developed. Anions derived from enantiomerically enriched thiophosphonamidates (2-thioxo-l,3,2-oxazaphosphorinanes) underwent smooth electrophilic substitutions with excellent diastereoselectivity for both cis and trans stereoisomers. Highly enantioselective synthesis of α-alkoxyphosphonates in either antipodal form can be achieved by the employment of highly diastereoselective alkylation with anions derived from the corresponding P-methoxymethyl analogs in the presence of HMPA or PMDTA. Implications for the aggregation states and reactive conformations of the anions are discussed.

Original languageEnglish (US)
Pages (from-to)11879-11897
Number of pages19
JournalJournal of the American Chemical Society
Volume117
Issue number48
DOIs
StatePublished - Jan 1 1995

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Alkylation
Anions
anion
Negative ions
Phosphorous Acids
substitution
Substitution reactions
Hempa
Organophosphonates
Stereoisomerism
Conformations
Agglomeration
Acids
acid

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions. / Denmark, Scott E; Chen, Chien Tien.

In: Journal of the American Chemical Society, Vol. 117, No. 48, 01.01.1995, p. 11879-11897.

Research output: Contribution to journalArticle

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