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The isolation of these compounds is rather challenging due to the reversibility of the reaction (elimination of alcohols). However, methylation of the sulfonamide moiety of the intermediate lithium salts and sulfur protection of the phosphorus atom prevent the elimination reaction. The resulting air\u2010stable <jats:italic>P<\/jats:italic>\u2010chiral diastereomeric 1\u2010alkoxy\u20102,3\u2010dihydrophosphole sulfide mixtures can be readily isolated and fully characterized. The diastereomers can be separated by crystallization. The 1\u2010alkoxy\u20102,3\u2010dihydrophosphole sulfides are readily reduced with Raney nickel to afford phosphorus(III) <jats:italic>P<\/jats:italic>\u2010stereogenic 1\u2010alkoxy\u20102,3\u2010dihydrophospholes with potential use in asymmetric homogeneous transition metal catalysis.<\/jats:p>","DOI":"10.1002\/chem.202300790","type":"journal-article","created":{"date-parts":[[2023,5,15]],"date-time":"2023-05-15T22:05:39Z","timestamp":1684188339000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Facile Synthesis of Enantiomerically Pure <i>P<\/i>\u2010Chiral 1\u2010Alkoxy\u20102,3\u2010dihydrophospholes via Nucleophilic P\u2010N Bond Cleavage of a 1\u2010Phospha\u20102\u2010azanorbornene"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2878-3620","authenticated-orcid":false,"given":"Kyzgaldak","family":"Ramazanova","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry Faculty of Chemistry and Mineralogy Leipzig University  Johannisallee 29 04103 Leipzig Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1335-0897","authenticated-orcid":false,"given":"Peter","family":"L\u00f6nnecke","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry Faculty of Chemistry and Mineralogy Leipzig University  Johannisallee 29 04103 Leipzig Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4267-0603","authenticated-orcid":false,"given":"Evamarie","family":"Hey\u2010Hawkins","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry Faculty of Chemistry and Mineralogy Leipzig University  Johannisallee 29 04103 Leipzig Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,6,6]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00029"},{"key":"e_1_2_8_2_1","first-page":"1445","author":"Knowles W. 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