{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T12:58:20Z","timestamp":1788440300331,"version":"build-2803163510"},"reference-count":90,"publisher":"Wiley","issue":"34","license":[{"start":{"date-parts":[[2019,7,2]],"date-time":"2019-07-02T00:00:00Z","timestamp":1562025600000},"content-version":"am","delay-in-days":347,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2018,7,20]],"date-time":"2018-07-20T00:00:00Z","timestamp":1532044800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["CHE-1339674"],"award-info":[{"award-number":["CHE-1339674"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["038550-02"],"award-info":[{"award-number":["038550-02"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["S10RR028859"],"award-info":[{"award-number":["S10RR028859"]}],"id":[{"id":"10.13039\/100000002","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":[[2018,8,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A direct (3+2) cycloaddition between alkenes and vinyl diazo reagents using either Cr or Ru photocatalysis is described. The intermediacy of a radical cation species enables a nucleophilic interception by vinyl diazo compounds, a departure from their traditional electrophilic behavior. A variety of cyclopentenes are synthesized using this method, and experimental insights implicate a direct cycloaddition instead of a cyclopropanation\/rearrangement process.<\/jats:p>","DOI":"10.1002\/anie.201805732","type":"journal-article","created":{"date-parts":[[2018,7,2]],"date-time":"2018-07-02T15:20:25Z","timestamp":1530544825000},"page":"11015-11019","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":74,"title":["Cyclopentene Annulations of Alkene Radical Cations with Vinyl Diazo Species Using Photocatalysis"],"prefix":"10.1002","volume":"57","author":[{"given":"Francisco J.","family":"Sarabia","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Georgia  Athens GA 30602 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiankun","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Georgia  Athens GA 30602 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9412-0713","authenticated-orcid":false,"given":"Eric M.","family":"Ferreira","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Georgia  Athens GA 30602 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,7,20]]},"reference":[{"key":"e_1_2_2_1_1","first-page":"273","volume-title":"Comprehensive Organic Synthesis\u2005II, Vol.\u20055","author":"Iwasawa N.","year":"2014"},{"key":"e_1_2_2_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2016.12.071"},{"key":"e_1_2_2_3_1","unstructured":"For recent reviews on the use of vinyl and enol diazocarbonyl compounds see:"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00324B"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201600099"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201701346"},{"key":"e_1_2_2_7_1","unstructured":"For seminal examples using vinyl diazocarbonyls see:"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)93966-2"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00095a031"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0160546"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9078094"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja407179c"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC04106J"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201501039"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701572"},{"key":"e_1_2_2_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201701572"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0036-1590885"},{"key":"e_1_2_2_17_1","unstructured":"For seminal examples using enol diazocarbonyls see:"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja3092399"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc48993k"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201605438"},{"key":"e_1_2_2_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201605438"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b02192"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201706639"},{"key":"e_1_2_2_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201706639"},{"key":"e_1_2_2_23_1","unstructured":"C=O and C=N bonds have also been utilized as the two-atom component to form heterocycles. For examples see:"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol016703i"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja029745q"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja106751t"},{"key":"e_1_2_2_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja808080h"},{"key":"e_1_2_2_28_1","unstructured":"For isolated cases of vinyl diazo nucleophilicity see:"},{"key":"e_1_2_2_29_2","unstructured":"Ref.\u2005[6b];"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja208965b"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201205692"},{"key":"e_1_2_2_31_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201205692"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo400419d"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5OB00696A"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409845"},{"key":"e_1_2_2_34_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201409845"},{"key":"e_1_2_2_35_1","unstructured":"The enol subunit of an enol diazocarbonyl has been invoked as a nucleophile (e.g. Mukaiyama aldol-type etc.). See Ref.\u2005[3a] for discussion and references."},{"key":"e_1_2_2_36_1","unstructured":"\u00a0"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4054866"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201306369"},{"key":"e_1_2_2_38_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201306369"},{"key":"e_1_2_2_39_1","unstructured":"For select reviews see:"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300503r"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200223"},{"key":"e_1_2_2_41_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201200223"},{"key":"e_1_2_2_42_2","doi-asserted-by":"publisher","DOI":"10.1039\/B913880N"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5OB01349F"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/cs400088e"},{"key":"e_1_2_2_45_1","unstructured":"\u00a0"},{"key":"e_1_2_2_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b07692"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201600084"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b01095"},{"key":"e_1_2_2_49_1","unstructured":"For reports of this process using triarylaminium catalysts see:"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00274a070"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/poc.610020802"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00126a007"},{"key":"e_1_2_2_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja107849y"},{"key":"e_1_2_2_54_1","unstructured":"\u00a0"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010020z"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00215a066"},{"key":"e_1_2_2_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b02723"},{"key":"e_1_2_2_58_1","unstructured":"The diastereoselectivity observed in the spirocycles3\u2009laand3\u2009malikely arises as a result of similar principles as those in the 1 2-transsubstituted alkenes. The diastereoselectivity of3\u2009qapresumably arises from preferential facial attack opposite the largetBu group."},{"key":"e_1_2_2_59_1","unstructured":"\u00a0"},{"key":"e_1_2_2_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60318a003"},{"key":"e_1_2_2_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198009473"},{"key":"e_1_2_2_61_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19800921204"},{"key":"e_1_2_2_62_1","unstructured":"Pyrazole formation was also observed in minute amounts in reactions using non-\u03b3-substituted vinyl diazo compounds."},{"key":"e_1_2_2_63_1","unstructured":"See the Supporting Information for details."},{"key":"e_1_2_2_64_1","unstructured":"Measurements: [Cr(Ph2phen)3]3+in CH3NO2(Ref.\u2005[16]); [Ru(bpz)3]2+in CH3CN (Ref.\u2005[11a]);1\u2009ain CH3NO2(Ref.\u2005[16]);2\u2009ain CH3NO2(see the Supporting Information)."},{"key":"e_1_2_2_65_1","unstructured":"Interestingly the (3+2) could also be mediated using Bauld's oxidizing triarylaminium catalyst albeit in moderate yield (47\u2009%). See the Supporting Information."},{"key":"e_1_2_2_66_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201712384"},{"key":"e_1_2_2_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201712384"},{"key":"e_1_2_2_67_1","unstructured":"The vinyldiazo2\u2009acould also be conceived as a one-electron reactant which has been invoked for non-vinyl diazo esters and other diazo compounds. This radical mode of nucleophilic attack essentially yields resonance forms of intermediate7\/8 which may or may not be more significant contributors to the hybrid depending on specific substitution patterns. For isolated examples invoking non-vinyl diazo esters and other diazo compounds as 1-electron reactants see:"},{"key":"e_1_2_2_68_2","unstructured":"Ref.\u2005[12b];"},{"key":"e_1_2_2_69_2","doi-asserted-by":"publisher","DOI":"10.1039\/P19960000769"},{"key":"e_1_2_2_70_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6PY02126C"},{"key":"e_1_2_2_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b11336"},{"key":"e_1_2_2_72_1","unstructured":"This regioselectivity could not be forced in the other direction by intramolecular tethering. See the Supporting Information for details."},{"key":"e_1_2_2_73_1","unstructured":"Both catalyst and light were necessary for this rearrangement."},{"key":"e_1_2_2_74_1","unstructured":"5-endoradical cyclizations are rare but have been reported."},{"key":"e_1_2_2_75_1","unstructured":"For additional mechanistic discussion see the Supporting Information."},{"key":"e_1_2_2_76_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC02185E"},{"key":"e_1_2_2_77_1","unstructured":"In contrast to the chromium-catalyzed (4+2) cycloadditions O2was not beneficial for this reaction."},{"key":"e_1_2_2_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0340735"},{"key":"e_1_2_2_79_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201503982"},{"key":"e_1_2_2_79_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201503982"},{"key":"e_1_2_2_80_1","unstructured":"Mg\/MeOH reduction afforded an approx. 1:1 mixture of diastereomers and the other diastereomer could then be obtained pure after ester cleavage. See the Supporting Information for details."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201805732","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201805732","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201805732","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.201805732","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201805732","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,17]],"date-time":"2023-09-17T02:13:46Z","timestamp":1694916826000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201805732"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,7,20]]},"references-count":90,"journal-issue":{"issue":"34","published-print":{"date-parts":[[2018,8,20]]}},"alternative-id":["10.1002\/anie.201805732"],"URL":"https:\/\/doi.org\/10.1002\/anie.201805732","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,7,20]]},"assertion":[{"value":"2018-05-17","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2018-07-20","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}