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- Title
Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis**.
- Authors
Das, Abir; Mandal, Rajib; Ravi Sankar, Harihara Subramanian; Kumaran, Subramani; Premkumar, J. Richard; Borah, Dipanti; Sundararaju, Basker
- Abstract
Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion of π‐coupling partner between M−C bond with high enantio‐induction remain elusive. Using commercially available Co(II) salt and chiral‐Salox ligands, we demonstrate an unusual protocol for the regio‐reversal, enantioselective C−H bond annulation of phosphinamide with bromoalkyne through desymmetrization. The reaction proceeds through ligand‐assisted enantiodetermining cyclocobaltation followed by regioselective insertion of bromoalkyne between Co−C, subsequent reductive elimination, and halogen exchange with carboxylate resulted in P‐stereogenic compounds in excellent ee (up to >99 %). The isolation of cobaltacycle involved in the catalytic cycle and the outcome of control experiments provide support for a plausible mechanism.
- Subjects
ANNULATION; LIGANDS (Chemistry); COBALT; HALOGENS; MOLECULES; SALT
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 6, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202315005