{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,29]],"date-time":"2026-01-29T13:42:45Z","timestamp":1769694165176,"version":"3.49.0"},"reference-count":24,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2023,6,1]],"date-time":"2023-06-01T00:00:00Z","timestamp":1685577600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003407","name":"Italian Ministry of Education, University, and Research (MIUR)\u2014Research Projects of National Interest (PRIN)","doi-asserted-by":"publisher","award":["2015T778JW"],"award-info":[{"award-number":["2015T778JW"]}],"id":[{"id":"10.13039\/501100003407","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A challenge in mimicking tyrosinase activity using model compounds is to reproduce its enantioselectivity. Good enantioselection requires rigidity and a chiral center close to the active site. In this study, the synthesis of a new chiral copper complex, [Cu2(mXPhI)]4+\/2+, based on an m-xylyl-bis(imidazole)-bis(benzimidazole) ligand containing a stereocenter with a benzyl residue directly bound on the copper chelating ring, is reported. Binding experiments show that the cooperation between the two metal centers is weak, probably due to steric hindrance given by the benzyl group. The dicopper(II) complex [Cu2(mXPhI)]4+ has catalytic activity in the oxidations of enantiomeric couples of chiral catechols, with an excellent discrimination capability for Dopa-OMe enantiomers and a different substrate dependence, hyperbolic or with substrate inhibition, for the L- or D- enantiomers, respectively. [Cu2(mXPhI)]4+ is active in a tyrosinase-like sulfoxidation of organic sulfides. The monooxygenase reaction requires a reducing co-substrate (NH2OH) and yields sulfoxide with significant enantiomeric excess (e.e.). Experiments with 18O2 and thioanisole yielded sulfoxide with 77% incorporation of 18O, indicating a reaction occurring mostly through direct oxygen transfer from the copper active intermediate to the sulfide. This mechanism and the presence of the chiral center of the ligand in the immediate copper coordination sphere are responsible for the good enantioselectivity observed.<\/jats:p>","DOI":"10.3390\/molecules28114487","type":"journal-article","created":{"date-parts":[[2023,6,2]],"date-time":"2023-06-02T02:16:48Z","timestamp":1685672208000},"page":"4487","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Asymmetric Sulfoxidation by a Tyrosinase Biomimetic Dicopper Complex with a Benzimidazolyl Derivative of L-Phenylalanine"],"prefix":"10.3390","volume":"28","author":[{"given":"Eliana","family":"Lo Presti","sequence":"first","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-0164-5543","authenticated-orcid":false,"given":"Fabio","family":"Schifano","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chiara","family":"Bacchella","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1824-1617","authenticated-orcid":false,"given":"Laura","family":"Santagostini","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Milano, Via Golgi 19, 20133 Milano, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7671-0506","authenticated-orcid":false,"given":"Luigi","family":"Casella","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8791-6446","authenticated-orcid":false,"given":"Enrico","family":"Monzani","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,6,1]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1016\/j.ccr.2016.07.009","article-title":"Small-molecule models of tyrosinase: From ligand hydroxylation to catalytic monooxygenation of external substrates","volume":"334","author":"Hamann","year":"2017","journal-title":"Coord. 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