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Herein, the first example of catalytic coordination\u2010induced asymmetric HAT reaction has been developed relying on a sequential (salen)Ti<jats:sup>III<\/jats:sup>\u2010initiated radical generation and (salen)Ti<jats:sup>IV<\/jats:sup>\u2010controlled enantioselective HAT process. The reaction transforms easily accessible glycidic esters, thioesters and amides to synthetically valuable formal formaldehyde aldol adducts in an enantioconvergent manner, along with broad scope and highly regio\u2010 and enantioselectivities.<\/jats:p>","DOI":"10.1002\/anie.202214111","type":"journal-article","created":{"date-parts":[[2022,10,21]],"date-time":"2022-10-21T05:14:58Z","timestamp":1666329298000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["(Salen)Titanium\u2010Catalyzed Asymmetric Hydrogen Atom Transfer for Epoxides Reduction"],"prefix":"10.1002","volume":"61","author":[{"given":"Zhongyun","family":"Xu","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jian","family":"Shen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Longfei","family":"Li","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wanjiao","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shengxiao","family":"Li","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Jiang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4702-5419","authenticated-orcid":false,"given":"Yong\u2010Qiang","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,11,15]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2009.07.001"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar100093z"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b08856"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC04112B"},{"key":"e_1_2_7_6_1","unstructured":"\u00a0"},{"key":"e_1_2_7_7_2","volume-title":"Free Radicals, Vol.\u20052","author":"Kochi J. 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