{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T18:52:22Z","timestamp":1792003942331,"version":"4.4.0"},"reference-count":86,"publisher":"American Chemical Society (ACS)","issue":"40","license":[{"start":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T00:00:00Z","timestamp":1790553600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["GM128570"],"award-info":[{"award-number":["GM128570"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,14]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We report herein an enantioselective total synthesis of (\u2212)-methyl gummiferolate, a complex diterpene natural product with a tetracyclic ent-atisane core including a bicyclo[2.2.2]octane subunit and three all-carbon quaternary centers. Gummiferolic acid has demonstrated potent plant growth-regulatory activity similar or superior to gibberellic acid. Using pattern recognition analysis, the tetracyclic ent-atisane core of (\u2212)-methyl gummiferolate was retrosynthetically traced back to chiral pool molecule (S)-perillaldehyde and a six-membered ring containing starting material which can be accessed using an enantioselective Diels\u2013Alder reaction with the Rawal diene. Our forward synthesis features a substrate-controlled stereoselective MHAT-initiated Baran reductive olefin cross coupling (BROC), a powerful radical cyclization approach, to close the six-membered B ring and an intramolecular alkylation to build the bicyclo[2.2.2]octane subunit. The BROC precursor was assembled in a convergent manner using a 1,2-addition of an alkyl lithium to a Weinreb amide derived from (S)-perillaldehyde. The alkyl lithium precursor was prepared from a known cyclohexenone (12) using key steps including CBS reduction, 2,3-Wittig\u2013Still rearrangement, and Appel iodination. Overall, (\u2212)-methyl gummiferolate was prepared in 18 steps from 12.<\/jats:p>","DOI":"10.1021\/jacs.6c15246","type":"journal-article","created":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T06:02:23Z","timestamp":1790575343000},"page":"42898-42903","source":"Crossref","is-referenced-by-count":0,"title":["Convergent Total Synthesis\nof (\u2212)-Methyl Gummiferolate\nEnabled by Pattern Recognition and Radical Cyclization"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-7684-9015","authenticated-orcid":true,"given":"Weizhao","family":"Zhao","sequence":"first","affiliation":[{"name":"Emory University , , , ,","place":["Atlanta, Georgia, United States, 30322"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingsong","family":"Zhen","sequence":"additional","affiliation":[{"name":"Emory University , , , ,","place":["Atlanta, Georgia, United States, 30322"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7956-6426","authenticated-orcid":true,"given":"Mingji","family":"Dai","sequence":"additional","affiliation":[{"name":"Emory University , , , ,","place":["Atlanta, Georgia, United States, 30322"]},{"name":"School of Medicine, Emory University , , , ,","place":["Atlanta, Georgia, United States, 30322"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,28]]},"reference":[{"key":"2026101414071787900_cit1","doi-asserted-by":"publisher","first-page":"1637","DOI":"10.1016\/S0031-9422(00)94658-2","article-title":"Gummiferolic acid, a new ent-atis-16-ene diterpenoid from Margotia gummifera","volume":"17","author":"Pinar","year":"1978","journal-title":"Phytochemistry"},{"key":"2026101414071787900_cit2a","doi-asserted-by":"publisher","first-page":"645","DOI":"10.1021\/np800657j","article-title":"Approach\nto the biosynthesis of atisine-type diterpenoid alkaloids","volume":"72","author":"Zhao","year":"2009","journal-title":"J. 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