{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T15:27:04Z","timestamp":1787412424957,"version":"build-2736575974"},"reference-count":46,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T00:00:00Z","timestamp":1786406400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T00:00:00Z","timestamp":1786406400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T00:00:00Z","timestamp":1786406400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100016047","name":"Science Fund of the Republic of Serbia","doi-asserted-by":"publisher","award":["7750119"],"award-info":[{"award-number":["7750119"]}],"id":[{"id":"10.13039\/501100016047","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Ministarstvo nauke, tehnolo?kog razvoja i inovacija","doi-asserted-by":"publisher","award":["451-03-33\/2026-03\/200168"],"award-info":[{"award-number":["451-03-33\/2026-03\/200168"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Ministarstvo nauke, tehnolo?kog razvoja i inovacija","doi-asserted-by":"publisher","award":["451-03-33\/2026-03\/200288"],"award-info":[{"award-number":["451-03-33\/2026-03\/200288"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,21]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>A reaction of thioesters and selenoesters with doubly stabilized carbenes generated from the corresponding diazo reagents under Rh or Cu catalysis affords products resulting from formal carbene insertion into the C(O)\u2013S and C(O)\u2013Se bonds. The generality of this transformation was demonstrated across a total of 37 examples. A complex reaction mechanism was proposed based on both the isolation of a key intermediate and DFT calculations for the overall reaction pathway. The resulting densely functionalized products, containing up to four different activating groups attached to the same carbon atom, can be readily converted into a variety of valuable compounds through selective and robust defunctionalization reactions.<\/jats:p>","DOI":"10.1021\/acs.joc.6c01632","type":"journal-article","created":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T22:01:43Z","timestamp":1786485703000},"page":"11550-11558","source":"Crossref","is-referenced-by-count":0,"title":["Reaction of Thioesters\nand Selenoesters with Diazo\nReagents: Formal Carbene Insertion into C\u2013S and C\u2013Se\nBonds"],"prefix":"10.1021","volume":"91","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-4100-3387","authenticated-orcid":true,"given":"Ivan","family":"Borkovic","sequence":"first","affiliation":[{"name":"University of Belgrade\u2212Faculty of Chemistry , Studentski trg 16 , POB 51, , 118,","place":["Belgrade, Serbia, 11158"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Milena","family":"Trmcic","sequence":"additional","affiliation":[{"name":"Innovative Centre Faculty of Chemistry Belgrade Ltd , Studentski trg 12 , ,","place":["Belgrade, Serbia, 11158"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5932-629X","authenticated-orcid":true,"given":"Zorana","family":"Ferjancic","sequence":"additional","affiliation":[{"name":"University of Belgrade\u2212Faculty of Chemistry , Studentski trg 16 , POB 51, , 118,","place":["Belgrade, Serbia, 11158"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0746-5754","authenticated-orcid":true,"given":"Maja","family":"Gruden","sequence":"additional","affiliation":[{"name":"University of Belgrade\u2212Faculty of Chemistry , Studentski trg 16 , POB 51, , 118,","place":["Belgrade, Serbia, 11158"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stepan","family":"Stepanovic","sequence":"additional","affiliation":[{"name":"Geneva University Hospitals and University of Geneva (Genomic Research Laboratory) , ,","place":["Geneva, Switzerland, 1206"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7654-3189","authenticated-orcid":true,"given":"Filip","family":"Bihelovic","sequence":"additional","affiliation":[{"name":"University of Belgrade\u2212Faculty of Chemistry , Studentski trg 16 , POB 51, , 118,","place":["Belgrade, Serbia, 11158"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,11]]},"reference":[{"key":"2026082211145009000_cit1a","doi-asserted-by":"publisher","first-page":"1353","DOI":"10.1021\/ja01084a034","article-title":"Dimethyloxosulfonium methylide ((CH3)2SOCH2) and dimethylsulfonium methylide\n((CH3)2SCH2). Formation and application\nto organic synthesis","volume":"87","author":"Corey","year":"1965","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit1b","doi-asserted-by":"publisher","first-page":"867","DOI":"10.1021\/ja00864a040","article-title":"Dimethylsulfoxonium methylide","volume":"84","author":"Corey","year":"1962","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit1c","doi-asserted-by":"publisher","first-page":"37125","DOI":"10.1039\/D5RA04921K","article-title":"A review on\nthe sulfur ylide-mediated Corey\u2013Chaykovsky reaction: a powerful\napproach to natural product synthesis","volume":"15","author":"Ammara","year":"2025","journal-title":"RSC Adv."},{"key":"2026082211145009000_cit2a","doi-asserted-by":"publisher","first-page":"69","DOI":"10.1039\/jr9320000069","article-title":"Degradation of quaternary ammonium\nsalts. Part V. Molecular rearrangement in related sulphur compounds","author":"Thomson","year":"1932","journal-title":"J. Chem. Soc."},{"key":"2026082211145009000_cit2b","doi-asserted-by":"publisher","first-page":"2118","DOI":"10.1055\/a-2050-4967","article-title":"Recent\nAdvances in Asymmetric [1,2]-Stevens-Type Rearrangement via Metal\nCarbenes","volume":"55","author":"Shi","year":"2023","journal-title":"Synthesis"},{"key":"2026082211145009000_cit3a","doi-asserted-by":"publisher","first-page":"4758","DOI":"10.1021\/ja01019a062","article-title":"An in vitro\nModel\nfor the Enzymatic Coupling of Farnesol","volume":"90","author":"Baldwin","year":"1968","journal-title":"J. Am.\nChem. Soc."},{"issue":"4","key":"2026082211145009000_cit3b","doi-asserted-by":"publisher","first-page":"417","DOI":"10.1016\/S0040-4039(01)98775-1","article-title":"Vinylsulfonium ylides\nas possible enzymic intemediates; exchange and rearrangement of a\nvinylsulfonium ylide","volume":"9","author":"Bates","year":"1968","journal-title":"Tetrahedron Lett."},{"key":"2026082211145009000_cit3c","article-title":"Sulfur Ylides\nin Organic Synthesis and Transition Metal Catalysis, In Modern Ylide\nChemistry","volume-title":"Structure Bonding (Berlin)","author":"Oost","year":"2017"},{"key":"2026082211145009000_cit3d","doi-asserted-by":"publisher","first-page":"4011","DOI":"10.1016\/j.tet.2016.11.045","article-title":"Transition metal-catalyzed [2,3]-sigmatropic\nrearrangements of ylides: An update of the most recent advances","volume":"73","author":"Sheng","year":"2017","journal-title":"Tetrahedron"},{"key":"2026082211145009000_cit4a","doi-asserted-by":"publisher","first-page":"693","DOI":"10.1021\/ol703058p","article-title":"Rh(II)-Catalyzed\nSommelet\u2013\nHauser Rearrangement","volume":"10","author":"Liao","year":"2008","journal-title":"Org. Lett."},{"key":"2026082211145009000_cit4b","doi-asserted-by":"publisher","first-page":"1210","DOI":"10.1021\/ol200091k","article-title":"Catalytic Thia-Sommelet\u2013Hauser\nRearrangement: Application to the Synthesis of Oxindoles","volume":"13","author":"Li","year":"2011","journal-title":"Org. Lett."},{"key":"2026082211145009000_cit4c","doi-asserted-by":"publisher","first-page":"5385","DOI":"10.1055\/a-1914-7261","article-title":"Recent Advances\nin the Generation of Onium Ylides for Sommelet\u2013Hauser Rearrangements","volume":"54","author":"Tayama","year":"2022","journal-title":"Synthesis"},{"key":"2026082211145009000_cit4d","doi-asserted-by":"publisher","first-page":"3427","DOI":"10.1039\/D2OB00218C","article-title":"Catalytic rearrangements of onium ylides in aromatic\nsystems","volume":"20","author":"Nair","year":"2022","journal-title":"Org. Biomol. Chem."},{"key":"2026082211145009000_cit5a","doi-asserted-by":"publisher","first-page":"994","DOI":"10.1002\/cber.19681010333","article-title":"Reaktionen des Diazomethans\nmit Diallylsulfid\nund Allyla\u0308thern unter Kupfersalz-Katalyse","volume":"101","author":"Kirmse","year":"1968","journal-title":"Chem. Ber."},{"key":"2026082211145009000_cit5b","doi-asserted-by":"publisher","first-page":"5094","DOI":"10.1021\/jo00338a008","article-title":"Highly effective catalytic methods for ylide generation\nfrom diazo compounds. Mechanism of the rhodium- and copper-catalyzed\nreactions with allylic compounds","volume":"46","author":"Doyle","year":"1981","journal-title":"J. Org. Chem."},{"key":"2026082211145009000_cit5c","doi-asserted-by":"publisher","first-page":"3895","DOI":"10.1055\/a-2119-5390","article-title":"Recent\nAdvances in the Asymmetric Doyle\u2013Kirmse Reaction","volume":"55","author":"Shi","year":"2023","journal-title":"Synthesis"},{"key":"2026082211145009000_cit5d","doi-asserted-by":"publisher","first-page":"941","DOI":"10.1016\/j.ccr.2009.12.005","article-title":"Catalytic [2,3]-sigmatropic rearrangement of sulfur ylide derived\nfrom metal carbene","volume":"254","author":"Zhang","year":"2010","journal-title":"Coord. Chem. Rev."},{"key":"2026082211145009000_cit6a","doi-asserted-by":"publisher","first-page":"93","DOI":"10.1039\/JR9470000093","article-title":"22. The rearrangement\nof 1-phenacyl-\u03b1-phenylethyldimethylammonium bromide","volume":"0","author":"Campbell","year":"1947","journal-title":"J. Chem. Soc."},{"key":"2026082211145009000_cit6b","doi-asserted-by":"publisher","first-page":"5179","DOI":"10.1021\/ja01140a058","article-title":"Nucleophilic Displacement via Frontal Attack. The Stereochemistry\nof the Stevens Rearrangement","volume":"74","author":"Brewster","year":"1952","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit6c","doi-asserted-by":"publisher","first-page":"155","DOI":"10.1002\/anie.196201551","article-title":"On the Mechanism of the Stevens Rearrangement","volume":"1","author":"Jenny","year":"1962","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026082211145009000_cit6d","doi-asserted-by":"publisher","first-page":"42","DOI":"10.1002\/jlac.19656830106","article-title":"Umlagerungen organischer Anionen, IV Stereochemischer\nAblauf der Isomerisation von Dimethyl-benzyl-[\u03b1-D]-aminoxyd\nzu O-Benzyl-[\u03b1-D]-N, N-dimethyl-hydroxylamin Ein Beitrag zur Frage der SNi-Substitution","volume":"683","author":"Scho\u0308llkopf","year":"1965","journal-title":"Justus Liebigs Ann.\nChem."},{"key":"2026082211145009000_cit6e","doi-asserted-by":"publisher","first-page":"866","DOI":"10.1021\/ja00956a064","article-title":"Transfer\nof Asymmetry from Nitrogen to Carbon in the Stevens Rearrangement","volume":"88","author":"Hill","year":"1966","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit6f","doi-asserted-by":"publisher","first-page":"4884","DOI":"10.1021\/ja01020a023","article-title":"Stereochemistry of 9-dimethylamino-9,10-dihydro-4,5-dimethylphenanthrene","volume":"90","author":"Joshua","year":"1968","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit6g","doi-asserted-by":"publisher","first-page":"116","DOI":"10.1002\/jlac.19485600105","article-title":"U\u0308ber die Stevens\u2019sche\nund Sommelet\u2019sche Umlagerung als Ylid-Reaktionen","volume":"560","author":"Wittig","year":"1948","journal-title":"Justus Liebigs Ann. Chem."},{"key":"2026082211145009000_cit6h","doi-asserted-by":"publisher","first-page":"1437","DOI":"10.1021\/ja01148a011","article-title":"Rearrangement of Benzyl Ethers to\nCarbinols by Potassium Amide. Mechanism of Isomerization of Carbanions\nInvolving 1,2-Shifts","volume":"73","author":"Hauser","year":"1951","journal-title":"J. Am. Chem. Soc."},{"key":"2026082211145009000_cit7","doi-asserted-by":"publisher","first-page":"781","DOI":"10.1002\/anie.196907811","article-title":"The Conservation of\nOrbital Symmetry","volume":"8","author":"Woodward","year":"1969","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026082211145009000_cit8a","doi-asserted-by":"publisher","first-page":"576b","DOI":"10.1039\/c2970000576b","article-title":"Simultaneous\nobservation of a radical pathway and retention in a Stevens rearrangement\nof a sulphonium ylide: significance for a general theory of ylide\nrearrangements","author":"Baldwin","year":"1970","journal-title":"J. Chem. Soc. D"},{"key":"2026082211145009000_cit8b","doi-asserted-by":"publisher","first-page":"543","DOI":"10.1039\/c39750000543","article-title":"The mechanism of the Stevens rearrangement","author":"Ollis","year":"1975","journal-title":"J. Chem. Soc., Chem. Commun."},{"key":"2026082211145009000_cit8c","doi-asserted-by":"publisher","first-page":"1009","DOI":"10.1039\/p19830001009","article-title":"Base catalyzed rearrangements involving\nylide intermediates. Part 15. The mechanism of the Stevens [1,2]-rearrangement","author":"Ollis","year":"1983","journal-title":"J. Chem. Soc., Perkin Trans. 1"},{"key":"2026082211145009000_cit9","doi-asserted-by":"publisher","first-page":"1477","DOI":"10.1002\/jlac.198019801004","article-title":"\u03b1-Oxosulfone, 3. Reaktionen acyclischer \u03b1-Oxosulfone","volume":"1980","author":"Schank","year":"1980","journal-title":"Liebigs Ann. Chem."},{"key":"2026082211145009000_cit10","doi-asserted-by":"publisher","first-page":"2023","DOI":"10.1002\/hlca.19650480823","article-title":"Re\u0301actions du diazome\u0301thane\nII. Transformation de la fonction N-(phe\u0301nylthio-carbonyle)\nde la N-(phe\u0301nylthio-carbonyl)-aniline avec production de phe\u0301nylthio-ace\u0301tanilide\npar insertion","volume":"48","author":"Baudet","year":"1965","journal-title":"Helv. Chim. Acta"},{"key":"2026082211145009000_cit11","doi-asserted-by":"publisher","first-page":"1017","DOI":"10.1039\/D1CC06041D","article-title":"Rhodium-catalyzed denitrogenative gem-difunctionalization\nof pyridotriazoles with thioesters:\nformal carbene insertion into C(O)\u2013S bonds","volume":"58","author":"Gao","year":"2022","journal-title":"Chem. Commun."},{"key":"2026082211145009000_cit12","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-27167-x","article-title":"Modular and stereoselective synthesis of tetrasubstituted vinyl sulfides\nleading to a library of AIEgens","volume":"12","author":"Liu","year":"2021","journal-title":"Nat. Commun."},{"key":"2026082211145009000_cit13","doi-asserted-by":"publisher","first-page":"2928","DOI":"10.1039\/D4QO00265B","article-title":"Blue light-mediated\ncarbene transfer reaction of thioesters with diazoesters: efficient\nsynthesis of tetrasubstituted Z-enol esters","volume":"11","author":"Wang","year":"2024","journal-title":"Org. Chem. Front."},{"key":"2026082211145009000_cit14","doi-asserted-by":"publisher","first-page":"439","DOI":"10.1039\/C7OB02597A","article-title":"Convenient synthesis\nof 2-amino-3-(arylthio) indoles via the Rh-catalyzed reaction of 3-diazoindol-2-imines\nwith thioesters","volume":"16","author":"Ma","year":"2018","journal-title":"Org. Biomol. Chem."},{"key":"2026082211145009000_cit15a","doi-asserted-by":"publisher","first-page":"15992","DOI":"10.1021\/acscatal.5c04499","article-title":"Construction and Asymmetric Skeletal\nRearrangement of Medium- Sized Rings: Divergent Synthesis of Pyrazole\/Pyrazolone-Annulated\nFrameworks","volume":"15","author":"Xu","year":"2025","journal-title":"ACS Catal."},{"key":"2026082211145009000_cit15b","doi-asserted-by":"publisher","first-page":"13253","DOI":"10.1021\/acs.orglett.5c04153","article-title":"A Synthetic Approach to Diverse Indole\/Oxindole-Annulated S-Heterocycles","volume":"27","author":"Xu","year":"2025","journal-title":"Org. Lett."},{"key":"2026082211145009000_cit16","doi-asserted-by":"publisher","first-page":"488","DOI":"10.1021\/acs.orglett.4c04495","article-title":"A Formal 1,2-Stevens Rearrangement\nof Thioester Ylides as a Single-Atom Molecular Editing Tool","volume":"27","author":"Borkovic","year":"2025","journal-title":"Org. Lett."},{"key":"2026082211145009000_cit17a","doi-asserted-by":"publisher","first-page":"21","DOI":"10.1038\/d41586-023-01735-1","article-title":"\u2019Almost magical\u2019: chemists\ncan now move single atoms in and out of a molecule\u2019s core","volume":"618","author":"Peplow","year":"2023","journal-title":"Nature"},{"key":"2026082211145009000_cit17b","doi-asserted-by":"publisher","DOI":"10.1126\/science.aat0805","article-title":"The importance of synthetic chemistry in the pharmaceutical\nindustry","volume":"363","author":"Campos","year":"2019","journal-title":"Science"},{"key":"2026082211145009000_cit17c","doi-asserted-by":"publisher","first-page":"11459","DOI":"10.1021\/acs.jmedchem.4c01347","article-title":"Rational Molecular\nEditing: A New Paradigm in Drug Discovery","volume":"67","author":"Ma","year":"2024","journal-title":"J.\nMed. Chem."},{"key":"2026082211145009000_cit18a","doi-asserted-by":"publisher","first-page":"11003","DOI":"10.1021\/acs.joc.4c00705","article-title":"Modular Synthesis\nof Tetrasubstituted\nVinyl Sulfides via One-Pot Sequential Carbene Transfer Reaction from\nThiols with \u03b1-Diazo Carbonyl Compounds","volume":"89","author":"Ma","year":"2024","journal-title":"J. Org. Chem."},{"key":"2026082211145009000_cit18b","doi-asserted-by":"publisher","first-page":"83","DOI":"10.1002\/ajoc.201600466","article-title":"RhII-Catalyzed\nCyclization of Ester\/Thioester-Containing N-Sulfonyl-1,2,3-triazoles:\nFacile Synthesis of Alkylidenephthalans and Alkylidenethiophthalans","volume":"6","author":"Sun","year":"2017","journal-title":"Asian J. Org. Chem."},{"key":"2026082211145009000_cit18c","doi-asserted-by":"publisher","first-page":"9967","DOI":"10.1002\/anie.201504013","article-title":"A Reaction of Triazoles with Thioesters to Produce\n\u03b2-Sulfanyl Enamides by Insertion of an Enamine Moiety into the\nSulfur\u2013Carbonyl Bond","volume":"54","author":"Miura","year":"2015","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026082211145009000_cit19","doi-asserted-by":"publisher","first-page":"2175","DOI":"10.1021\/acs.orglett.2c00477","article-title":"Highly Stereoselective\nSynthesis of Tetrasubstituted Vinyl Selenides via Rhodium-Catalyzed\n[1,4]-Acyl Migration of Selenoesters and Diazo Compounds","volume":"24","author":"Liu","year":"2022","journal-title":"Org. Lett."},{"key":"2026082211145009000_cit20","unstructured":"Velde, G. t.; Bickelhaupt, F. M.; Baerends, E. J.; et al.\n          Chemistry\nwith ADF, Theoretical Chemistry; Vrije Universiteit, 2023."}],"container-title":["The Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.joc.6c01632","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/91\/33\/11550\/66503643\/acs.joc.6c01632.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/91\/33\/11550\/66503643\/acs.joc.6c01632.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T15:15:35Z","timestamp":1787411735000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/joceah\/article\/91\/33\/11550\/5252995\/Reaction-of-Thioesters-and-Selenoesters-with-Diazo"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,11]]},"references-count":46,"journal-issue":{"issue":"33","published-online":{"date-parts":[[2026,8,11]]},"published-print":{"date-parts":[[2026,8,21]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.joc.6c01632","relation":{},"ISSN":["0022-3263","1520-6904"],"issn-type":[{"value":"0022-3263","type":"print"},{"value":"1520-6904","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,11]]}}}