{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,26]],"date-time":"2026-04-26T21:42:08Z","timestamp":1777239728217,"version":"3.51.4"},"reference-count":53,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2026,4,16]],"date-time":"2026-04-16T00:00:00Z","timestamp":1776297600000},"content-version":"vor","delay-in-days":15,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"},{"start":{"date-parts":[[2026,4,1]],"date-time":"2026-04-01T00:00:00Z","timestamp":1775001600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPlusChem"],"published-print":{"date-parts":[[2026,4]]},"abstract":"<jats:p>\n                    Preparative experiments including the alkylation of diphenylthiophosphinic acid with a series of C\n                    <jats:sub>1<\/jats:sub>\n                    \u2010C\n                    <jats:sub>4<\/jats:sub>\n                    haloalkenes at 75\/115\u00b0C in the presence of triethylamine in toluene suggested chemoselective formation of the corresponding S\u2010 (thiolic) ester. No O\u2010(thionic) ester was formed. For this, we wished to clarify the confusion regarding the outcome of such alkylations described in the literature. A few analogous derivatives were also synthesized and characterized for comparison. First in the literature, crystal structures of two thiolic esters were analyzed in detail. The alkylation led to non\u2010centrosymmetric crystal structures. Moreover, the two isostructural thiolic compounds formed chiral crystals, a rather unusual feature of achiral molecules. Weak interactions such as C\u2013H \u2026 O bridges and dispersion dominate and tailor the structure of the crystals. As regards the mechanism, three possible pathways were investigated at the B3LYP\/6\u201031G(d,p)\/PCM[toluene] level of theory. The activation enthalpy for the rate\u2010determining step was significantly lower for the triethylamine\u2010catalyzed route than for the base\u2010free variation. Moreover, in the base\u2010catalyzed protocol, the difference of 30.8\u2009kJ mol\n                    <jats:sup>\u20131<\/jats:sup>\n                    between the enthalpy of activation for the S and O\u2010alkylations justified the S\u2010selectivity. The pathway involving the anion from the thiophosphinic acid was found unfavorable and hence was excluded.\n                  <\/jats:p>","DOI":"10.1002\/cplu.70142","type":"journal-article","created":{"date-parts":[[2026,4,16]],"date-time":"2026-04-16T11:05:26Z","timestamp":1776337526000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chemoselective Alkylating Esterification of Thiophosphinic Acids: An Experimental and Theoretical Study"],"prefix":"10.1002","volume":"91","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5366-472X","authenticated-orcid":false,"given":"Gy\u00f6rgy","family":"Keglevich","sequence":"first","affiliation":[{"name":"Department of Organic Chemistry and Technology Faculty of Chemical Technology and Biotechnology Budapest University of Technology and Economics  Budapest Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dorka","family":"Nagy","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry and Technology Faculty of Chemical Technology and Biotechnology Budapest University of Technology and Economics  Budapest Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3224-8847","authenticated-orcid":false,"given":"Zolt\u00e1n","family":"Mucsi","sequence":"additional","affiliation":[{"name":"Faculty of Material and Chemical Sciences University of Miskolc  Miskolc Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8855-730X","authenticated-orcid":false,"given":"Konstantin","family":"Karaghiosoff","sequence":"additional","affiliation":[{"name":"Department Chemie  Ludwig\u2010Maximilian University  Munich Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"M\u00e1ty\u00e1s","family":"Czugler","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry and Technology Faculty of Chemical Technology and Biotechnology Budapest University of Technology and Economics  Budapest Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9589-6652","authenticated-orcid":false,"given":"L\u00e1szl\u00f3","family":"Drahos","sequence":"additional","affiliation":[{"name":"MS Proteomics Research Group HUN\u2010REN Research Centre for Natural Sciences  Budapest  Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"G\u00f6m\u00f6ry","family":"\u00c1gnes","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry and Technology Faculty of Chemical Technology and Biotechnology Budapest University of Technology and Economics  Budapest Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2026,4,16]]},"reference":[{"key":"e_1_2_9_2_1","first-page":"367","volume-title":"Organophosphorus Chemistry","author":"Quin L. 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