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Ion exchange with excess [NBu<jats:sub>4<\/jats:sub>][\u0394\u2010TRISPHAT] (\u0394\u2010TRISPHAT=\u0394\u2010P(o\u2010C<jats:sub>6<\/jats:sub>Cl<jats:sub>4<\/jats:sub>O<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>) followed by chromatography on silica removed [NBu<jats:sub>4<\/jats:sub>][OTf] and gave mixtures of syn\u2010 and anti\u2010[Mes*P(Me)CH<jats:sub>2<\/jats:sub>CHPh][\u0394\u2010TRISPHAT]\u22c5x[NBu<jats:sub>4<\/jats:sub>][\u0394\u2010TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P\u2010C cleavage to yield a hyperconjugation\u2010stabilized carbocation, pyramidal inversion promoted by \u03c3\u2010interaction of the P lone pair with the neighboring \u03b2\u2010carbocation, and ring closure with inversion of configuration at P.<\/jats:p>","DOI":"10.1002\/anie.202110753","type":"journal-article","created":{"date-parts":[[2021,11,10]],"date-time":"2021-11-10T07:25:03Z","timestamp":1636529103000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Configurational Lability at Tetrahedral Phosphorus: <i>syn\/anti<\/i>\u2010Isomerization of a P\u2010Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus"],"prefix":"10.1002","volume":"61","author":[{"given":"Ryan M.","family":"Tipker","sequence":"first","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jake A.","family":"Muldoon","sequence":"additional","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel H.","family":"Pham","sequence":"additional","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Balazs R.","family":"Varga","sequence":"additional","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Russell P.","family":"Hughes","sequence":"additional","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8438-8166","authenticated-orcid":false,"given":"David S.","family":"Glueck","sequence":"additional","affiliation":[{"name":"6128 Burke Laboratory Department of Chemistry Dartmouth College  Hanover NH 03755 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gary J.","family":"Balaich","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of California, San Diego  9500 Gilman Drive La Jolla CA 92093 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arnold L.","family":"Rheingold","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of California, San Diego  9500 Gilman Drive La Jolla CA 92093 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,11,23]]},"reference":[{"key":"e_1_2_2_1_1","volume-title":"Stereochemistry of Organic Compounds","author":"Eliel E. 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