{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T15:58:54Z","timestamp":1789660734903,"version":"4.0.1"},"reference-count":83,"publisher":"Wiley","issue":"31","license":[{"start":{"date-parts":[[2022,6,10]],"date-time":"2022-06-10T00:00:00Z","timestamp":1654819200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000928","name":"Welch Foundation","doi-asserted-by":"publisher","award":["E-0044"],"award-info":[{"award-number":["E-0044"]}],"id":[{"id":"10.13039\/100000928","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R01GM077635"],"award-info":[{"award-number":["R01GM077635"]}],"id":[{"id":"10.13039\/100000057","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":[[2022,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report here \u201csandwich\u201d diimine\u2010copper(I) catalysts for C(sp<jats:sup>3<\/jats:sup>)\u2212H bond functionalization. Reactions of alkanes and ethers with trimethylsilyldiazomethane, ethyl diazoacetate, and trifluoromethyl\u2010diazomethane have been demonstrated. We also report C(sp<jats:sup>3<\/jats:sup>)\u2212H bond methylation, benzylation, and diphenylmethylation by diazomethane, aryldiazomethanes, and diphenyldiazomethane. These reactions are rare examples of base\u2010metal catalyzed, intermolecular C(sp<jats:sup>3<\/jats:sup>)\u2212H functionalizations by employing unactivated diazo compounds. Electrophilicity and unique steric environment of \u201csandwich\u201d\u2010copper catalysts are likely reasons for their catalytic efficiency.<\/jats:p>","DOI":"10.1002\/anie.202200334","type":"journal-article","created":{"date-parts":[[2022,5,20]],"date-time":"2022-05-20T16:31:06Z","timestamp":1653064266000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["\u201cSandwich\u201d Diimine\u2010Copper Catalysts for C\u2212H Functionalization by Carbene Insertion"],"prefix":"10.1002","volume":"61","author":[{"given":"Kristine","family":"Klimovica","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd. Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julius X.","family":"Heidlas","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd. Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Irvin","family":"Romero","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd. Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thanh V.","family":"Le","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd. Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2642-2992","authenticated-orcid":false,"given":"Olafs","family":"Daugulis","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Houston  3585 Cullen Blvd. Houston TX USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,6,10]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202001224"},{"key":"e_1_2_7_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202001224"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00507"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC04676K"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CS00086K"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703743"},{"key":"e_1_2_7_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201703743"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.6b00032"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7SC03610H"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aao4798"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00182a"},{"key":"e_1_2_7_11_1","unstructured":"\u00a0"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00382"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00221F"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2010.05.073"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900239n"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr078364y"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201901168"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT03450G"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34406h"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200390290"},{"key":"e_1_2_7_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200390261"},{"key":"e_1_2_7_21_1","unstructured":"\u00a0"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b02428"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/b901170f"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.12.97"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00425"},{"key":"e_1_2_7_26_1","unstructured":"Selected examples:"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-018-0799-2"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja510573v"},{"key":"e_1_2_7_29_1","unstructured":"\u00a0"},{"key":"e_1_2_7_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00808a088"},{"key":"e_1_2_7_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja016798j"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00718"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/b911981g"},{"key":"e_1_2_7_34_1","unstructured":"\u00a0"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CS00542K"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202007001"},{"key":"e_1_2_7_36_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202007001"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201402945"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja508586t"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408102"},{"key":"e_1_2_7_39_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201408102"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC01476K"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201809344"},{"key":"e_1_2_7_41_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201809344"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201604211"},{"key":"e_1_2_7_42_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201604211"},{"key":"e_1_2_7_43_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC05432D"},{"key":"e_1_2_7_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2020.06.031"},{"key":"e_1_2_7_45_1","unstructured":"\u00a0"},{"key":"e_1_2_7_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b04344"},{"key":"e_1_2_7_47_2","doi-asserted-by":"publisher","DOI":"10.1039\/j39680002276"},{"key":"e_1_2_7_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00406"},{"key":"e_1_2_7_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201511954"},{"key":"e_1_2_7_49_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201511954"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.6b00487"},{"key":"e_1_2_7_51_1","unstructured":"\u00a0"},{"key":"e_1_2_7_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/om400704h"},{"key":"e_1_2_7_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja502130w"},{"key":"e_1_2_7_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/cs5016029"},{"key":"e_1_2_7_55_1","unstructured":"\u00a0"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja047935q"},{"key":"e_1_2_7_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010401)40:7<1288::AID-ANIE1288>3.0.CO;2-6"},{"key":"e_1_2_7_57_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010401)113:7<1328::AID-ANGE1328>3.0.CO;2-P"},{"key":"e_1_2_7_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010917)40:18<3392::AID-ANIE3392>3.0.CO;2-Y"},{"key":"e_1_2_7_58_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010917)113:18<3495::AID-ANGE3495>3.0.CO;2-6"},{"key":"e_1_2_7_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic801443y"},{"key":"e_1_2_7_60_1","unstructured":"Reaction of a more electrophilic carbene source ethyl diazoacetate with dioxane catalyzed by a hydrotris(3-mesityl)pyrazolylborate Cu complex gave C\u2212H insertion product in 20\u2009% yield. Please see ref.\u2005[5b]."},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0446294"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c11645"},{"key":"e_1_2_7_63_1","unstructured":"For enantioselective engineered cytochrome P450 enzyme-catalyzed amine \u03b1-C\u2212H trifluoroethylation please see ref.\u2005[7a]."},{"key":"e_1_2_7_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr200060g"},{"key":"e_1_2_7_65_1","unstructured":"Non-selective photochemical insertions of methylene into C\u2212H bonds are known. Addition of transition metal such as rhodium shuts down C\u2212H insertion reactivity in favor of ylide formation."},{"key":"e_1_2_7_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19420751229"},{"key":"e_1_2_7_67_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)61878-6"},{"key":"e_1_2_7_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00186a007"},{"key":"e_1_2_7_69_1","unstructured":"\u00a0"},{"key":"e_1_2_7_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200600811"},{"key":"e_1_2_7_71_2","unstructured":"Reactions of TMSCHN2with dioxane give higher yields if lower catalyst loadings are employed. Please see Table\u2005S-1 in Supporting Information."},{"key":"e_1_2_7_72_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2014.10.009"},{"key":"e_1_2_7_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c04533"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202200334","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202200334","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202200334","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,24]],"date-time":"2023-08-24T00:29:07Z","timestamp":1692836947000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202200334"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,6,10]]},"references-count":83,"journal-issue":{"issue":"31","published-print":{"date-parts":[[2022,8]]}},"alternative-id":["10.1002\/anie.202200334"],"URL":"https:\/\/doi.org\/10.1002\/anie.202200334","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,6,10]]},"assertion":[{"value":"2022-01-10","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-06-10","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202200334"}}