{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,27]],"date-time":"2026-10-27T20:27:58Z","timestamp":1793132878679,"version":"4.5.0"},"reference-count":109,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2023,1,10]],"date-time":"2023-01-10T00:00:00Z","timestamp":1673308800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22271299 and 22261132514"],"award-info":[{"award-number":["22271299 and 22261132514"]}],"id":[{"id":"10.13039\/501100001809","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":[[2023,2,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We have developed a new strategy for controllable single and double difluoromethylene (CF<jats:sub>2<\/jats:sub>) formal insertions into C\u2212H bonds of aldehydes with nearly full selectivity under transition\u2010metal\u2010free conditions. The key to the success of controllable CF<jats:sub>2<\/jats:sub>insertions lies in the well\u2010defined formation of 2,2\u2010difluoroenolsilyl ether and 2,2,3,3\u2010tetrafluorocyclopropanolsilyl ether intermediates using difluorocarbene reagent TMSCF<jats:sub>2<\/jats:sub>Br (TMS=trimethylsilyl). These two intermediates can react with various electrophiles including proton sources and various halogenation reagents, allowing for the access to diverse arrays of ketones containing difluoromethylene (CF<jats:sub>2<\/jats:sub>) and tetrafluoroethylene (CF<jats:sub>2<\/jats:sub>CF<jats:sub>2<\/jats:sub>) units. The first synthesis of relatively stable 2,2,3,3\u2010tetrafluorocyclopropanolsilyl ethers has been achieved, which offers a new platform to explore other unknown chemical space.<\/jats:p>","DOI":"10.1002\/anie.202217088","type":"journal-article","created":{"date-parts":[[2022,12,15]],"date-time":"2022-12-15T05:32:37Z","timestamp":1671082357000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["Transition\u2010Metal\u2010Free Controllable Single and Double Difluoromethylene Formal Insertions into C\u2212H Bonds of Aldehydes with TMSCF<sub>2<\/sub>Br"],"prefix":"10.1002","volume":"62","author":[{"given":"An","family":"Liu","sequence":"first","affiliation":[{"name":"Key Laboratory of Organofluorine Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Ling-Ling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2296-8835","authenticated-orcid":false,"given":"Chuanfa","family":"Ni","sequence":"additional","affiliation":[{"name":"Key Laboratory of Organofluorine Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Ling-Ling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiqiang","family":"Xie","sequence":"additional","affiliation":[{"name":"Key Laboratory of Organofluorine Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Ling-Ling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3537-0207","authenticated-orcid":false,"given":"Jinbo","family":"Hu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Organofluorine Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Ling-Ling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,1,10]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00392"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.0c00830"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.9b01877"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.isci.2020.101467"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1038\/s43586-021-00042-1"},{"key":"e_1_2_8_7_1","unstructured":"\u00a0"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.7b01788"},{"key":"e_1_2_8_9_1","unstructured":"\u00a0"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/b610738a"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2015.01.007"},{"key":"e_1_2_8_12_1","unstructured":"\u00a0"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00360G"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.4155\/fmc-2019-0309"},{"key":"e_1_2_8_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b04457"},{"key":"e_1_2_8_16_1","unstructured":"\u00a0"},{"key":"e_1_2_8_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c03104"},{"key":"e_1_2_8_18_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.abm8868"},{"key":"e_1_2_8_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2022.109972"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abg9065"},{"key":"e_1_2_8_21_1","unstructured":"For selected reviews for the synthesis of compounds containing CF2unit see:"},{"key":"e_1_2_8_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(96)00311-0"},{"key":"e_1_2_8_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201800532"},{"key":"e_1_2_8_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201905475"},{"key":"e_1_2_8_25_1","unstructured":"For selected reviews for the synthesis of compounds containing CF2CF2unit see:"},{"key":"e_1_2_8_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201701590"},{"key":"e_1_2_8_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500465n"},{"key":"e_1_2_8_28_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_8_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr941141k"},{"key":"e_1_2_8_30_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0033-1340856"},{"key":"e_1_2_8_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00079"},{"key":"e_1_2_8_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2018.02.056"},{"key":"e_1_2_8_33_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2019.01.016"},{"key":"e_1_2_8_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00244"},{"key":"e_1_2_8_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC04029D"},{"key":"e_1_2_8_36_1","unstructured":"For selected examples observing uncontrollable byproducts see:"},{"key":"e_1_2_8_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/p19800000661"},{"key":"e_1_2_8_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00264a043"},{"key":"e_1_2_8_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(00)80465-0"},{"key":"e_1_2_8_40_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2009.10.011"},{"key":"e_1_2_8_41_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2746"},{"key":"e_1_2_8_42_1","unstructured":"For examples achieving sequential CF2insertions see:"},{"key":"e_1_2_8_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00037a057"},{"key":"e_1_2_8_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(99)00247-X"},{"key":"e_1_2_8_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC05018C"},{"key":"e_1_2_8_46_2","unstructured":"Ref.\u20055a."},{"key":"e_1_2_8_47_1","unstructured":"For representative examples achieving single CF2insertion see:"},{"key":"e_1_2_8_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol400122k"},{"key":"e_1_2_8_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b12003"},{"key":"e_1_2_8_50_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aan1411"},{"key":"e_1_2_8_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201807873"},{"key":"e_1_2_8_51_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201807873"},{"key":"e_1_2_8_52_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-019-0331-9"},{"key":"e_1_2_8_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b02001"},{"key":"e_1_2_8_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.202000297"},{"key":"e_1_2_8_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c09505"},{"key":"e_1_2_8_56_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2CC00975G"},{"key":"e_1_2_8_57_1","unstructured":"\u00a0"},{"key":"e_1_2_8_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202115467"},{"key":"e_1_2_8_58_3","doi-asserted-by":"crossref","DOI":"10.1002\/ange.202115467","volume":"134","year":"2022","journal-title":"Angew. Chem."},{"key":"e_1_2_8_59_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2020.131370"},{"key":"e_1_2_8_60_1","unstructured":"\u00a0"},{"key":"e_1_2_8_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5OB00855G"},{"key":"e_1_2_8_62_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC07677H"},{"key":"e_1_2_8_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00346"},{"key":"e_1_2_8_64_1","unstructured":"For selected examples see:"},{"key":"e_1_2_8_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202116190"},{"key":"e_1_2_8_65_3","doi-asserted-by":"crossref","DOI":"10.1002\/ange.202116190","volume":"134","year":"2022","journal-title":"Angew. Chem."},{"key":"e_1_2_8_66_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC01574E"},{"key":"e_1_2_8_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b03024"},{"key":"e_1_2_8_68_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7QO00430C"},{"key":"e_1_2_8_69_1","unstructured":"For selected examples see:"},{"key":"e_1_2_8_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00801a022"},{"key":"e_1_2_8_71_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0034-1379599"},{"key":"e_1_2_8_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b09888"},{"key":"e_1_2_8_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b00488"},{"key":"e_1_2_8_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b02726"},{"key":"e_1_2_8_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b00097"},{"key":"e_1_2_8_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b01567"},{"key":"e_1_2_8_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b02085"},{"key":"e_1_2_8_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.2c00958"},{"key":"e_1_2_8_79_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2000.1366"},{"key":"e_1_2_8_80_1","unstructured":"\u00a0"},{"key":"e_1_2_8_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010023b"},{"key":"e_1_2_8_82_2","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.17.25"},{"key":"e_1_2_8_83_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.6b01739"},{"key":"e_1_2_8_84_1","unstructured":"For selected examples by our group see:"},{"key":"e_1_2_8_85_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0CC04548A"},{"key":"e_1_2_8_86_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201306703"},{"key":"e_1_2_8_86_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201306703"},{"key":"e_1_2_8_87_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201611823"},{"key":"e_1_2_8_87_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201611823"},{"key":"e_1_2_8_88_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201900763"},{"key":"e_1_2_8_88_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201900763"},{"key":"e_1_2_8_89_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b03520"},{"key":"e_1_2_8_90_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202103428"},{"key":"e_1_2_8_91_2","unstructured":"Ref.\u200513;"},{"key":"e_1_2_8_92_2","unstructured":"Ref.\u200517i;"},{"key":"e_1_2_8_93_2","unstructured":"Ref.\u20055a."},{"key":"e_1_2_8_94_1","unstructured":"For recent examples by other groups see:"},{"key":"e_1_2_8_95_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202100812"},{"key":"e_1_2_8_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.1c00577"},{"key":"e_1_2_8_97_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c10205"},{"key":"e_1_2_8_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.1c02603"},{"key":"e_1_2_8_99_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1OB00511A"},{"key":"e_1_2_8_100_2","doi-asserted-by":"publisher","DOI":"10.1055\/a-1507-5878"},{"key":"e_1_2_8_101_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC01132D"},{"key":"e_1_2_8_102_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.1c02305"},{"key":"e_1_2_8_103_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(01)00477-8"}],"container-title":["Angewandte Chemie International 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