{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T07:39:14Z","timestamp":1792136354322,"version":"4.4.0"},"reference-count":37,"publisher":"American Chemical Society (ACS)","issue":"23","license":[{"start":{"date-parts":[[2026,6,8]],"date-time":"2026-06-08T00:00:00Z","timestamp":1780876800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["2316541"],"award-info":[{"award-number":["2316541"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R35GM134897"],"award-info":[{"award-number":["R35GM134897"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000082","name":"Division of Graduate Education","doi-asserted-by":"publisher","award":["DGE-2444107"],"award-info":[{"award-number":["DGE-2444107"]}],"id":[{"id":"10.13039\/100000082","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006734","name":"Princeton University","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100006734","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,6,17]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Multisubstituted alkenes are valuable structural motifs that also serve as key intermediates in complexity-building transformations; however, their stereoselective synthesis remains a longstanding challenge. Alkenyl bromides are appealing coupling handles for alkene synthesis, though their application would be greatly enhanced if they could be coupled directly with alkyl radicals derived from feedstock alcohols. Herein, we report a nickel metallaphotoredox-enabled deoxygenative cross-coupling of alkenyl bromides with alcohols, providing a direct, modular approach to multisubstituted alkenes. This transformation exhibits a broad substrate scope across both alcohol and alkenyl bromide partners, delivering over 30 multisubstituted alkenes. Moreover, we developed a complementary stereoselective bromoalkenylation from readily synthesized gem-dibromoolefins to address the limited availability of stereodefined alkenyl bromides. In the presence of a phthalimide additive, selective monofunctionalization enables access to over 40 stereodefined alkenyl bromides, providing a general and stereoselective pathway to these otherwise difficult-to-access intermediates. Direct access to alkenyl bromides enables piecewise stereoselective assembly of multisubstituted alkenes through sequential alcohol coupling or stereoretentive Suzuki\u2013Miyaura reactions. These strategies are illustrated via iterative cross-coupling sequences and the total synthesis of (+)-sponalisolide B.<\/jats:p>","DOI":"10.1021\/jacs.6c09135","type":"journal-article","created":{"date-parts":[[2026,6,8]],"date-time":"2026-06-08T10:18:48Z","timestamp":1780913928000},"page":"23499-23505","source":"Crossref","is-referenced-by-count":1,"title":["Piecewise Stereoselective\nAssembly of Multisubstituted\nAlkenes"],"prefix":"10.1021","volume":"148","author":[{"given":"Eli","family":"Jones","sequence":"first","affiliation":[{"name":"Merck Center for Catalysis at Princeton University , , ,","place":["Princeton, New Jersey, United States, 08544"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7676-2840","authenticated-orcid":true,"given":"Robert T.","family":"Martin","sequence":"additional","affiliation":[{"name":"Merck Center for Catalysis at Princeton University , , ,","place":["Princeton, New Jersey, United States, 08544"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6447-0587","authenticated-orcid":true,"given":"David W. C.","family":"MacMillan","sequence":"additional","affiliation":[{"name":"Merck Center for Catalysis at Princeton University , , ,","place":["Princeton, New Jersey, United States, 08544"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,8]]},"reference":[{"issue":"5","key":"2026073023194648300_cit1","doi-asserted-by":"publisher","first-page":"1258","DOI":"10.1021\/acs.jnatprod.8b01022","article-title":"A Systematic Cheminformatics Analysis of Functional\nGroups Occurring in Natural Products","volume":"82","author":"Ertl","year":"2019","journal-title":"J. Nat.\nProd."},{"key":"2026073023194648300_cit2","volume-title":"Additions to and Substitutions at C-C \u03c0-Bonds","author":"Knochel","year":"2014"},{"issue":"16","key":"2026073023194648300_cit3","doi-asserted-by":"publisher","first-page":"3370","DOI":"10.3390\/molecules30163370","article-title":"Trisubstituted Alkenes\nas Valuable Building Blocks","volume":"30","author":"Tobrman","year":"2025","journal-title":"Molecules"},{"issue":"4","key":"2026073023194648300_cit4","doi-asserted-by":"publisher","first-page":"863","DOI":"10.1021\/cr00094a007","article-title":"The Wittig Olefination\nReaction and Modifications Involving\nPhosphoryl-Stabilized Carbanions. Stereochemistry, Mechanism, and\nSelected Synthetic Aspects","volume":"89","author":"Maryanoff","year":"1989","journal-title":"Chem. Rev."},{"key":"2026073023194648300_cit5","doi-asserted-by":"publisher","first-page":"216827","DOI":"10.1016\/j.ccr.2025.216827","article-title":"Challenges\nin Olefin Metathesis: Past, Present and Future","volume":"542","author":"Brotons-Rufes","year":"2025","journal-title":"Coord. Chem. Rev."},{"issue":"34","key":"2026073023194648300_cit6","doi-asserted-by":"publisher","first-page":"4071","DOI":"10.1039\/D1CC00596K","article-title":"Recent Advances in the Stereoselective\nSynthesis of Acyclic All-Carbon Tetrasubstituted Alkenes","volume":"57","author":"Buttard","year":"2021","journal-title":"Chem. Commun."},{"issue":"17","key":"2026073023194648300_cit7","doi-asserted-by":"publisher","first-page":"5701","DOI":"10.1021\/jacs.8b02834","article-title":"Decarboxylative\nHydroalkylation of\nAlkynes","volume":"140","author":"Till","year":"2018","journal-title":"J. Am. Chem. Soc."},{"issue":"32","key":"2026073023194648300_cit8","doi-asserted-by":"publisher","first-page":"17557","DOI":"10.1021\/jacs.3c06479","article-title":"Stereoselective\nSynthesis of Trisubstituted Alkenes\nvia Copper Hydride-Catalyzed Alkyne Hydroalkylation","volume":"145","author":"Kutateladze","year":"2023","journal-title":"J. Am. Chem. Soc."},{"issue":"36","key":"2026073023194648300_cit9","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202300626","article-title":"Julia-Kocienski\nOlefination in the\nSynthesis of Trisubstituted Alkenes: Recent Progress","volume":"26","author":"Ouzounthanasis","year":"2023","journal-title":"Eur. J. Org. Chem."},{"issue":"14","key":"2026073023194648300_cit10","doi-asserted-by":"publisher","first-page":"5611","DOI":"10.1021\/acs.orglett.9b01959","article-title":"Triphosgene and DMAP\nas Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols","volume":"21","author":"Ganiu","year":"2019","journal-title":"Org. 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Soc."},{"issue":"33","key":"2026073023194648300_cit14","doi-asserted-by":"publisher","first-page":"11602","DOI":"10.1021\/ja506094d","article-title":"Photoredox\n\u03b1-Vinylation of \u03b1-Amino Acids\nand N -Aryl Amines","volume":"136","author":"Noble","year":"2014","journal-title":"J. Am.\nChem. Soc."},{"issue":"22","key":"2026073023194648300_cit15","doi-asserted-by":"publisher","first-page":"7399","DOI":"10.1002\/chem.201601320","article-title":"Cross-Electrophile Coupling of Vinyl\nHalides with Alkyl Halides","volume":"22","author":"Johnson","year":"2016","journal-title":"Chem. - Eur. 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Nat.\nProd."},{"issue":"6","key":"2026073023194648300_cit24","doi-asserted-by":"publisher","first-page":"2216","DOI":"10.1021\/jo061346g","article-title":"A Mild Synthesis\nof Vinyl Halides and gem-Dihalides\nUsing Triphenyl Phosphite-Halogen-Based Reagents","volume":"72","author":"Spaggiari","year":"2007","journal-title":"J. Org. Chem."},{"issue":"24","key":"2026073023194648300_cit25","doi-asserted-by":"publisher","first-page":"8799","DOI":"10.1021\/ja503944n","article-title":"Catalytic\nAnti-Markovnikov Hydrobromination\nof Alkynes","volume":"136","author":"Uehling","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"36","key":"2026073023194648300_cit26","doi-asserted-by":"publisher","first-page":"14760","DOI":"10.1021\/ja307771d","article-title":"Ruthenium-Catalyzed\nTransformation of Aryl and Alkenyl Triflates to Halides","volume":"134","author":"Imazaki","year":"2012","journal-title":"J. Am. Chem. 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Soc."},{"issue":"3","key":"2026073023194648300_cit29","doi-asserted-by":"publisher","first-page":"2698","DOI":"10.1021\/acscatal.5c08196","article-title":"Solvent-Controlled Monoselective Suzuki-Miyaura Cross-Coupling\nof Symmetrical 1,1-Dichloroalkenes: Scope and Origin of Selectivity","volume":"16","author":"Konowalchuk","year":"2026","journal-title":"ACS Catal."},{"issue":"9","key":"2026073023194648300_cit30","doi-asserted-by":"publisher","first-page":"3570","DOI":"10.1016\/j.ejmech.2011.05.021","article-title":"Design, Synthesis\nand Antiproliferative Activities of Biarylolefins Based on Polyhydroxylated\nand Carbohydrate Scaffolds","volume":"46","author":"Novoa","year":"2011","journal-title":"Eur. J. Med. Chem."},{"issue":"5","key":"2026073023194648300_cit31","doi-asserted-by":"publisher","first-page":"0737","DOI":"10.1055\/s-2000-6626","article-title":"A Modified\nSuzuki Reaction of 1,1-Dibromo-1-Alkenes","volume":"2000","author":"Shen","year":"2000","journal-title":"Synlett"},{"issue":"02","key":"2026073023194648300_cit32","doi-asserted-by":"publisher","first-page":"0254","DOI":"10.1055\/s-2001-10776","article-title":"Suzuki Arylation\nof 1,1-Dibromo-1-Alkenes: Synthesis of Tetra-Substituted Alkenes","volume":"2001","author":"Bauer","year":"2001","journal-title":"Synlett"},{"issue":"25","key":"2026073023194648300_cit33","doi-asserted-by":"publisher","first-page":"6052","DOI":"10.1039\/D5OB00646E","article-title":"Synthetic Methodologies to Access Skipped Dienes: A\nFocus on the Catalytic Systems","volume":"23","author":"Renzi","year":"2025","journal-title":"Org. Biomol.\nChem."},{"issue":"6592","key":"2026073023194648300_cit34","doi-asserted-by":"publisher","first-page":"532","DOI":"10.1126\/science.abn1885","article-title":"Accelerating reaction generality\nand mechanistic insight through additive mapping","volume":"376","author":"Prieto Kullmer","year":"2022","journal-title":"Science"},{"issue":"37","key":"2026073023194648300_cit35","doi-asserted-by":"publisher","first-page":"33991","DOI":"10.1021\/jacs.5c11247","article-title":"Reactivity Studies of Bipyridine-Ligated Nickel(I)\nand Nickel(0) Complexes Inform the Mechanism in Modern Cross-Coupling\nReactions","volume":"147","author":"Raab","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"32","key":"2026073023194648300_cit36","doi-asserted-by":"publisher","first-page":"6237","DOI":"10.1016\/S0040-4039(00)01038-8","article-title":"Practical Methylation of Aryl Halides\nby Suzuki-Miyaura Coupling","volume":"41","author":"Gray","year":"2000","journal-title":"Tetrahedron Lett."},{"issue":"6","key":"2026073023194648300_cit37","doi-asserted-by":"publisher","first-page":"1022","DOI":"10.1039\/C7QO01091E","article-title":"Racemic\nTrinorsesquiterpenoids from the Beihai Sponge Spongia officinalis: Structure and Biomimetic Total Synthesis","volume":"5","author":"Sun","year":"2018","journal-title":"Org. Chem. Front."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c09135","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/23499\/66272481\/jacs.6c09135.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/23\/23499\/66272481\/jacs.6c09135.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T03:19:56Z","timestamp":1785467996000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/23\/23499\/5233530\/Piecewise-Stereoselective-Assembly-of"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,8]]},"references-count":37,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2026,6,8]]},"published-print":{"date-parts":[[2026,6,17]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c09135","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,8]]}}}