biostudies-literatureSingh DNational Institute of General Medical SciencesNIGMS NIH HHSNational Science Foundatione202216000https://www.ebi.ac.uk/biostudies/studies/S-EPMC9908849biostudies-literatureUnknown62(8)Alkynes and 1,3-dienes are among the most readily available precursors for organic synthesis. We report two distinctly different, catalyst-dependent, modes of regio- and enantioselective cycloaddition reactions between these classes of compounds providing rapid access to highly functionalized 1,4-cyclohexadienes or cyclobutenes from the same precursors. Complexes of an earth abundant metal, cobalt, with several commercially available chiral bisphosphine ligands with narrow bite angles catalyze [4+2]-cycloadditions between a 1,3-diene and an alkyne giving a cyclohexa-1,4-diene in excellent chemo-, regio- and enantioselectivities. In sharp contrast, complex of a finely tuned phosphino-oxazoline ligand promotes unique [2+2]-cycloaddition between the alkyne and the terminal double bond of the Angewandte Chemie (International ed. in English)Chemodivergent, Regio- and Enantioselective Cycloaddition Reactions between 1,3-Dienes and Alkynes.PMC9908849CHE-1900141R35 GM139545-01R35 GM139545RajanBabu TVSingh DfalseChemodivergent, Regio- and Enantioselective Cycloaddition Reactions between 1,3-Dienes and Alkynes.Alkynes and 1,3-dienes are among the most readily available precursors for organic synthesis. We report two distinctly different, catalyst-dependent, modes of regio- and enantioselective cycloaddition reactions between these classes of compounds providing rapid access to highly functionalized 1,4-cyclohexadienes or cyclobutenes from the same precursors. Complexes of an earth abundant metal, cobalt, with several commercially available chiral bisphosphine ligands with narrow bite angles catalyze [4+2]-cycloadditions between a 1,3-diene and an alkyne giving a cyclohexa-1,4-diene in excellent chemo-, regio- and enantioselectivities. In sharp contrast, complex of a finely tuned phosphino-oxazoline ligand promotes unique [2+2]-cycloaddition between the alkyne and the terminal double bond of the 2023-01-01T00:00:00Z2023 Feb2026-03-17T16:00:09.745Z2025-04-06T15:23:55.139ZS-EPMC99088493652061910.1002/anie.202216000