{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,28]],"date-time":"2026-10-28T22:08:30Z","timestamp":1793225310908,"version":"4.5.0"},"reference-count":102,"publisher":"Wiley","issue":"29","license":[{"start":{"date-parts":[[2025,5,23]],"date-time":"2025-05-23T00:00:00Z","timestamp":1747958400000},"content-version":"am","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"},{"start":{"date-parts":[[2025,5,23]],"date-time":"2025-05-23T00:00:00Z","timestamp":1747958400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["R35GM147387"],"award-info":[{"award-number":["R35GM147387"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE\u20102400087"],"award-info":[{"award-number":["CHE\u20102400087"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["OAC\u20102117681"],"award-info":[{"award-number":["OAC\u20102117681"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["OAC\u20102138259"],"award-info":[{"award-number":["OAC\u20102138259"]}],"id":[{"id":"10.13039\/100000001","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":[[2025,7,14]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Cooperative catalysis with an enzyme and a small\u2010molecule photocatalyst has recently emerged as a potentially general activation mode to advance novel biocatalytic reactions with synthetic utility. Herein, we report cooperative photobiocatalysis involving an engineered nonheme Fe enzyme and a tailored photoredox catalyst to achieve enantioconvergent decarboxylative azidation, thiocyanation, and isocyanation of redox\u2010active esters via a radical mechanism. We repurposed and further evolved metapyrocatechase (MPC), a nonheme Fe extradiol dioxygenase not previously studied in new\u2010to\u2010nature biocatalysis, for the enantioselective C\u2500N\n                    <jats:sub>3<\/jats:sub>\n                    , C\u2500SCN, and C\u2500NCO bond formation via an enzymatic Fe\u2500X intermediate (X\u2550N\n                    <jats:sub>3<\/jats:sub>\n                    , NCS, and NCO). A range of primary, secondary, and tertiary alkyl radical precursors were effectively converted by our engineered MPC, allowing the syntheses of organic azides, thiocyanates, and isocyanates with good to excellent enantiocontrol. Further derivatization of these products furnished valuable compounds including enantioenriched amines, triazoles, ureas, and SCF\n                    <jats:sub>3<\/jats:sub>\n                    \u2010containing products. DFT and MD simulations shed light on the mechanism as well as the binding poses of the alkyl radical intermediate in the enzyme active site and the \u03c0\u2010facial selectivity in the enantiodetermining radical rebound. Overall, cooperative photometallobiocatalysis with nonheme Fe enzymes provides a means to develop challenging asymmetric radical transformations eluding small\u2010molecule catalysis.\n                  <\/jats:p>","DOI":"10.1002\/anie.202506361","type":"journal-article","created":{"date-parts":[[2025,5,14]],"date-time":"2025-05-14T10:10:11Z","timestamp":1747217411000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["Cooperative Photometallobiocatalysis: Nonheme Fe Enzyme\u2010Catalyzed Enantioconvergent Radical Decarboxylative Azidation, Thiocyanation, and Isocyanation of Redox\u2010Active Esters"],"prefix":"10.1002","volume":"64","author":[{"given":"Liu\u2010Peng","family":"Zhao","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ken","family":"Lin","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pei\u2010Pei","family":"Xie","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Pittsburgh  Pittsburgh PA 15260 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huichong","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hengye","family":"Xiang","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Pittsburgh  Pittsburgh PA 15260 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunlong","family":"Zhao","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peng","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Pittsburgh  Pittsburgh PA 15260 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4956-2034","authenticated-orcid":false,"given":"Yang","family":"Yang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of California Santa Barbara  Santa Barbara CA 93106 USA"},{"name":"Biomolecular Science and Engineering (BMSE) Program University of California Santa Barbara  Santa Barbara CA 93106 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,5,23]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-019-0385-5"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adh8615"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.4c00247"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00719"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00767"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.4c00129"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202419262"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c03879"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-024-01494-0"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202412862"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202211199"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-024-08138-w"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adg2420"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-024-07284-5"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c05949"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c04661"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-023-06822-x"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c02752"},{"key":"e_1_2_7_19_1","first-page":"1118","volume":"2024","author":"Xing Z.","year":"2024","journal-title":"Nature"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abk1603"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c04937"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-023-00986-5"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-024-01608-8"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abj2830"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-024-00507-7"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-024-00536-2"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c14310"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-00633-7"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202407111"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2024.06.010"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202312893"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020044l"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-00561-6"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00582"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature20569"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaw1143"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c11462"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/B913880N"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300503r"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00018"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00057"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0504412102"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature04544"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchembio.1625"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchembio.2112"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201907245"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-019-1020-y"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41589-019-0355-x"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b04691"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-15777-w"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201914994"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-27999-1"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41589-021-00944-x"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202201115"},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.2214512120"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-49147-7"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.6b01173"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchembio.1438"},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202301370"},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.2c02872"},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.RA120.016019"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1111\/febs.16722"},{"key":"e_1_2_7_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.2c00115"},{"key":"e_1_2_7_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c07224"},{"key":"e_1_2_7_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.3c02617"},{"key":"e_1_2_7_66_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c01375"},{"key":"e_1_2_7_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00383"},{"key":"e_1_2_7_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c01124"},{"key":"e_1_2_7_69_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature14127"},{"key":"e_1_2_7_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.6b00214"},{"key":"e_1_2_7_71_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07330"},{"key":"e_1_2_7_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c05881"},{"key":"e_1_2_7_73_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-020-00551-4"},{"key":"e_1_2_7_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c02012"},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00265"},{"key":"e_1_2_7_76_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.4c00188"},{"key":"e_1_2_7_77_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202301205"},{"key":"e_1_2_7_78_1","doi-asserted-by":"publisher","DOI":"10.31635\/ccschem.020.202000435"},{"key":"e_1_2_7_79_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC02049H"},{"key":"e_1_2_7_80_1","doi-asserted-by":"publisher","DOI":"10.1016\/1010-6030(89)87066-2"},{"key":"e_1_2_7_81_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0969-2126(99)80006-9"},{"key":"e_1_2_7_82_1","first-page":"213","volume-title":"Int. Congr. Ser","author":"Ishida T.","year":"2002"},{"key":"e_1_2_7_83_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-024-01257-7"},{"key":"e_1_2_7_84_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja004153y"},{"key":"e_1_2_7_85_1","doi-asserted-by":"publisher","DOI":"10.1021\/bi049317s"},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0014-5793(03)01439-X"},{"key":"e_1_2_7_87_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chembiol.2004.08.012"},{"key":"e_1_2_7_88_1","doi-asserted-by":"publisher","DOI":"10.3389\/fpls.2019.00695"},{"key":"e_1_2_7_89_1","doi-asserted-by":"publisher","DOI":"10.1016\/0922-338X(96)88811-8"},{"key":"e_1_2_7_90_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja101721e"},{"key":"e_1_2_7_91_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201410045"},{"key":"e_1_2_7_92_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja038656q"},{"key":"e_1_2_7_93_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaf6123"},{"key":"e_1_2_7_94_1","doi-asserted-by":"publisher","DOI":"10.1371\/journal.pcbi.1002708"},{"key":"e_1_2_7_95_1","doi-asserted-by":"publisher","DOI":"10.1093\/oxfordjournals.jbchem.a124753"},{"key":"e_1_2_7_96_1","doi-asserted-by":"publisher","DOI":"10.1021\/sb300037w"},{"key":"e_1_2_7_97_1","doi-asserted-by":"publisher","DOI":"10.1002\/0471212466"},{"key":"e_1_2_7_98_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200400657"},{"key":"e_1_2_7_99_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500193b"},{"key":"e_1_2_7_100_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00564"},{"key":"e_1_2_7_101_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.257.5072.942"},{"key":"e_1_2_7_102_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja001901a"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202506361","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202506361","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,11,29]],"date-time":"2025-11-29T18:19:17Z","timestamp":1764440357000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202506361"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,23]]},"references-count":102,"journal-issue":{"issue":"29","published-print":{"date-parts":[[2025,7,14]]}},"alternative-id":["10.1002\/anie.202506361"],"URL":"https:\/\/doi.org\/10.1002\/anie.202506361","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,5,23]]},"assertion":[{"value":"2025-03-19","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-05-14","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-05-23","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202506361"}}