Chemodivergent, 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‐cy...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-02, Vol.62 (8), p.e202216000-n/a
Main Authors: Singh, Dipshi, RajanBabu, T. V.
Format: Article
Language:English
Subjects:
1,3-Dienes
Alkynes
Asymmetric Catalysis
Catalysts
Chemical synthesis
Chemodivergent Reactions
Cobalt
Cycloaddition
Dienes
Enantiomers
Ligands
Precursors
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Summary: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 diene giving a highly functionalized cyclobutene in excellent regio‐ and enantioselectivities. Reported herein are ligand controlled, chemodivergent [4+2] or [2+2] cycloaddition reactions between readily available 1,3‐dienes and alkynes. These reactions, catalyzed by cationic CoI proceed with high regio‐ and enantioselectivies to give nearly enantiopure functionalized 1,4‐ cyclohexadienes or cyclobutenes from the same starting materials.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202216000