Carbanion-accelerated claisen rearrangements: Asymmetric induction with chiral phosphorus-stabilized anions

Scott E Denmark, John E. Marlin, G. Rajendra

Research output: Contribution to journalArticle

Abstract

The carbanion-accelerated Claisen rearrangement has been extended to include phosphorus carbanion-stabilizing groups. The appropriately substituted allyl vinyl ethers are synthesized by the nucleophilic addition of allyl oxides to phosphorus-substituted allenes, which are obtained in one step from simple starting materials. The phosphorus-stabilized, carbanion-accelerated Claisen rearrangements proceed rapidly at room temperature in high yield, and the rearrangements are highly site- and stereoselective. The first examples of asymmetric induction in the Claisen rearrangement with chiral, phosphorus, anion-stabilizing groups are described. The observed asymmetric induction is highly dependent on the structure of the auxiliary and the metal counterion involved. Both internal and relative diastereoselectivity are high. A model for the observed sense of internal diastereoselectivity is proposed that is founded in the current understanding of the structure of phosphorus-stabilized anions.

Original languageEnglish (US)
Pages (from-to)66-82
Number of pages17
JournalJournal of Organic Chemistry
Volume78
Issue number1
DOIs
StatePublished - Jan 4 2013

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ASJC Scopus subject areas

  • Organic Chemistry

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