{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T19:52:54Z","timestamp":1790365974426,"version":"4.1.0"},"reference-count":51,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"6711","content-domain":{"domain":["www.science.org"],"crossmark-restriction":true},"short-container-title":["Science"],"published-print":{"date-parts":[[2024,8,23]]},"abstract":"<jats:p>\n            Samarium diiodide (SmI\n            <jats:sub>2<\/jats:sub>\n            ) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong Sm\n            <jats:sup>III<\/jats:sup>\n            \u2013O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover. However, such approaches give rise to complex catalyst speciation and intrinsically limit the synthetic scope. Herein, we leveraged a mild and selective protonolysis strategy to achieve samarium-catalyzed, intermolecular reductive cross-coupling of ketones and acrylates with broad scope. The modularity of our approach allows rational control of selectivity based on solvent, p\n            <jats:italic>K<\/jats:italic>\n            <jats:sub>a<\/jats:sub>\n            (where\n            <jats:italic>K<\/jats:italic>\n            <jats:sub>a<\/jats:sub>\n            is the acid dissociation constant), and the samarium coordination sphere and provides a basis for future developments in catalytic and electrocatalytic lanthanide chemistry.\n          <\/jats:p>","DOI":"10.1126\/science.adp5777","type":"journal-article","created":{"date-parts":[[2024,8,22]],"date-time":"2024-08-22T17:59:05Z","timestamp":1724349545000},"page":"847-853","update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":44,"title":["Reductive samarium (electro)catalysis enabled by Sm\n            <sup>III<\/sup>\n            -alkoxide protonolysis"],"prefix":"10.1126","volume":"385","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0150-5396","authenticated-orcid":true,"given":"Emily A.","family":"Boyd","sequence":"first","affiliation":[{"name":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-8125-5850","authenticated-orcid":true,"given":"Chungkeun","family":"Shin","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David J.","family":"Charboneau","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6610-4414","authenticated-orcid":true,"given":"Jonas C.","family":"Peters","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8244-9300","authenticated-orcid":true,"given":"Sarah E.","family":"Reisman","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00528a029"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr400685r"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(97)00008-7"},{"key":"e_1_3_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo052268k"},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo4028243"},{"key":"e_1_3_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c04210"},{"key":"e_1_3_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr030017a"},{"key":"e_1_3_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902151"},{"key":"e_1_3_2_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1RA08163B"},{"key":"e_1_3_2_11_2","doi-asserted-by":"crossref","unstructured":"A. K. Dey S. Majhi \u201cRole of samarium in organic synthesis\u201d in Rare Earth Elements B. Basu B. Banerjee Eds. (de Gruyter 2023) pp. 119\u2013140.","DOI":"10.1515\/9783110788082-007"},{"key":"e_1_3_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b01219"},{"key":"e_1_3_2_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2OB00907B"},{"key":"e_1_3_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00254"},{"key":"e_1_3_2_15_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-019-1134-2"},{"key":"e_1_3_2_16_2","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-023-00292-9"},{"key":"e_1_3_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c03352"},{"key":"e_1_3_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol049129u"},{"key":"e_1_3_2_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201703394"},{"key":"e_1_3_2_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol8019692"},{"key":"e_1_3_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c08288"},{"key":"e_1_3_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b11532"},{"key":"e_1_3_2_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202301045"},{"key":"e_1_3_2_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0013-4686(02)00844-7"},{"key":"e_1_3_2_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(97)00263-3"},{"key":"e_1_3_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja962331a"},{"key":"e_1_3_2_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol050256f"},{"key":"e_1_3_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/cs400587s"},{"key":"e_1_3_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b13119"},{"key":"e_1_3_2_30_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1991-20916"},{"key":"e_1_3_2_31_2","doi-asserted-by":"publisher","DOI":"10.1080\/00397919108021598"},{"key":"e_1_3_2_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)92221-4"},{"key":"e_1_3_2_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39930000499"},{"key":"e_1_3_2_34_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.200429"},{"key":"e_1_3_2_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c09580"},{"key":"e_1_3_2_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201900956"},{"key":"e_1_3_2_37_2","doi-asserted-by":"publisher","DOI":"10.1039\/P19880001669"},{"key":"e_1_3_2_38_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)00839-9"},{"key":"e_1_3_2_39_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-023-01073-5"},{"key":"e_1_3_2_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol202403q"},{"key":"e_1_3_2_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/0471758078"},{"key":"e_1_3_2_42_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1992-21544"},{"key":"e_1_3_2_43_2","first-page":"157","volume":"13","author":"Le Chatelier H. L.","year":"1888","unstructured":"H. L. Le Chatelier, Annales des Mines 13, 157 (1888).","journal-title":"Annales des Mines"},{"key":"e_1_3_2_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(97)10222-2"},{"key":"e_1_3_2_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00408a041"},{"key":"e_1_3_2_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202200370"},{"key":"e_1_3_2_47_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0034-1378867"},{"key":"e_1_3_2_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)85909-2"},{"key":"e_1_3_2_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200800876"},{"key":"e_1_3_2_50_2","unstructured":"P. Attia \u201cCyclic voltammetry simulator\u201d (GitHub 2024); https:\/\/github.com\/petermattia\/Cyclic-Voltammetry-Simulator."},{"key":"e_1_3_2_51_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(96)00861-7"},{"key":"e_1_3_2_52_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(94)88329-7"}],"container-title":["Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.science.org\/doi\/pdf\/10.1126\/science.adp5777","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,8,22]],"date-time":"2024-08-22T17:59:23Z","timestamp":1724349563000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.science.org\/doi\/10.1126\/science.adp5777"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,8,23]]},"references-count":51,"journal-issue":{"issue":"6711","published-print":{"date-parts":[[2024,8,23]]}},"alternative-id":["10.1126\/science.adp5777"],"URL":"https:\/\/doi.org\/10.1126\/science.adp5777","relation":{},"ISSN":["0036-8075","1095-9203"],"issn-type":[{"value":"0036-8075","type":"print"},{"value":"1095-9203","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,8,23]]},"assertion":[{"value":"2024-04-01","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-07-23","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-08-22","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}