{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["146(28)"],"submitter":["Tsitopoulou M"],"funding":["Universit?t Basel"],"pubmed_abstract":["1,4-Palladium migration has been widely used for the functionalization of remote C-H bonds. However, this mechanism has been limited to aryl halide precursors. This work reports an unprecedented Pd<sup>0</sup>-catalyzed cyclobutanation protocol producing valuable fused cyclobutanes starting from cycloalkenyl (pseudo)halides. This reaction takes place via alkenyl-to-alkyl 1,4-Pd migration, followed by intramolecular Heck coupling. The method performs best with cyclohexenyl precursors, giving access to a variety of substituted bicyclo[4,2,0]octenes. Reactants containing an <i>N</i>-methyl or methoxy group give rise to fused azetidines or oxetanes, respectively, via the same mechanism. Kinetic and deuterium-labeling studies point to a rate-limiting C(sp<sup>3</sup>)-H activation step."],"journal":["Journal of the American Chemical Society"],"pagination":["18811-18816"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC11258686"],"repository":["biostudies-literature"],"pubmed_title":["1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings."],"pmcid":["PMC11258686"],"pubmed_authors":["Thesmar P","Baudoin O","Clemenceau A","Tsitopoulou M"],"additional_accession":[]},"is_claimable":false,"name":"1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings.","description":"1,4-Palladium migration has been widely used for the functionalization of remote C-H bonds. However, this mechanism has been limited to aryl halide precursors. This work reports an unprecedented Pd<sup>0</sup>-catalyzed cyclobutanation protocol producing valuable fused cyclobutanes starting from cycloalkenyl (pseudo)halides. This reaction takes place via alkenyl-to-alkyl 1,4-Pd migration, followed by intramolecular Heck coupling. The method performs best with cyclohexenyl precursors, giving access to a variety of substituted bicyclo[4,2,0]octenes. Reactants containing an <i>N</i>-methyl or methoxy group give rise to fused azetidines or oxetanes, respectively, via the same mechanism. Kinetic and deuterium-labeling studies point to a rate-limiting C(sp<sup>3</sup>)-H activation step.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Jul","modification":"2025-04-06T22:43:07.827Z","creation":"2025-04-06T22:43:07.827Z"},"accession":"S-EPMC11258686","cross_references":{"pubmed":["38968581"],"doi":["10.1021/jacs.4c04701"]}}