Inversion of Configuration at the Phosphorus Nucleophile in the Diastereoselective and Enantioselective Synthesis of P-Stereogenic syn-Phosphiranes from Chiral Epoxides

Angewandte Chemie
Jake A MuldoonArnold L Rheingold

Abstract

Nucleophilic substitution results in inversion of configuration at the electrophilic carbon center (SN 2) or racemization (SN 1). The stereochemistry of the nucleophile is rarely considered, but phosphines, which have a high barrier to pyramidal inversion, attack electrophiles with retention of configuration at P. Surprisingly, cyclization of bifunctional secondary phosphine alkyl tosylates proceeded under mild conditions with inversion of configuration at the nucleophile to yield P-stereogenic syn-phosphiranes. DFT studies suggested that the novel stereochemistry results from acid-promoted tosylate dissociation to yield an intermediate phosphenium-bridged cation, which undergoes syn-selective cyclization.

References

Nov 1, 1996·The Journal of Organic Chemistry·Xinhua LiPeter P. Gaspar
Apr 3, 2003·Journal of the American Chemical Society·Katharine D CooneyYong Zhao
Jun 28, 2011·Chemical Communications : Chem Comm·Arne FicksLee J Higham
Aug 12, 2015·Angewandte Chemie·J Philipp Wagner, Peter R Schreiner

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Citations

Mar 19, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Tanuja TewariSamir H Chikkali
Aug 14, 2019·Journal of the American Chemical Society·Michael B GeesonChristopher C Cummins

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