{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T19:36:07Z","timestamp":1788204967216,"version":"build-2803163510"},"reference-count":60,"publisher":"Wiley","issue":"40","license":[{"start":{"date-parts":[[2023,8,24]],"date-time":"2023-08-24T00:00:00Z","timestamp":1692835200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001412","name":"Council of Scientific and Industrial Research, India","doi-asserted-by":"publisher","award":["02(0422)\/21\/EMR-II"],"award-info":[{"award-number":["02(0422)\/21\/EMR-II"]}],"id":[{"id":"10.13039\/501100001412","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2023,10,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The control of the reactivity of diazo compounds is commonly achieved by the choice of a suitable catalyst, e.g. via stabilization of singlet carbenes or radical intermediates. Herein, we report on the light\u2010promoted reactivity of cyclic diazo imides with thiols, where the choice of solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), a carbene is formed initially and engages in a cascade C\u2212H functionalization\/thiolation reaction to deliver indane\u2010fused pyrrolidines in good to excellent yields. When switching to acetonitrile solvent, the carbene pathway is shut down and an unusual reduction of the diazo compound occurs under otherwise identical reaction conditions, where the aryl thiol acts as reductant. A combined set of experimental and computational studies was carried out to obtain mechanistic understanding and to support that indane formation proceeds via the insertion of a triplet carbene, while the reduction of diazo imides proceeds via an electron transfer process.<\/jats:p>","DOI":"10.1002\/anie.202309184","type":"journal-article","created":{"date-parts":[[2023,7,28]],"date-time":"2023-07-28T18:50:24Z","timestamp":1690570224000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":34,"title":["Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent\u2010Dependent Reactivity of Cyclic Diazo Imides"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7370-1084","authenticated-orcid":false,"given":"Yaseen","family":"Hussain","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Jammu Jagti, NH-44  Nagrota Bypass Jammu 181221, J&amp;K India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9362-7755","authenticated-orcid":false,"given":"Claire","family":"Empel","sequence":"additional","affiliation":[{"name":"RWTH Aachen University Institute of Organic Chemistry  Landoltweg 1 52074 Aachen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0247-4384","authenticated-orcid":false,"given":"Rene M.","family":"Koenigs","sequence":"additional","affiliation":[{"name":"RWTH Aachen University Institute of Organic Chemistry  Landoltweg 1 52074 Aachen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8779-0652","authenticated-orcid":false,"given":"Pankaj","family":"Chauhan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Jammu Jagti, NH-44  Nagrota Bypass Jammu 181221, J&amp;K India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,8,24]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"crossref","unstructured":"R.\u2005A. 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