Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis**
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Berichtigung: Correction to “Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis”
- Volume 136Issue 25Angewandte Chemie
- First Published online: May 7, 2024
Abir Das
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorRajib Mandal
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorHarihara Subramanian Ravi Sankar
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorDr. Subramani Kumaran
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorDr. J. Richard Premkumar
PG & Research Department of Chemistry, Bishop Heber College, 620017 Tiruchirappalli, Tamil Nadu, India
Search for more papers by this authorDipanti Borah
Department of Chemistry, Indian Institute of Technology Bombay, Powai, 400076 Mumbai, Maharashtra, India
Search for more papers by this authorCorresponding Author
Prof. Dr. Basker Sundararaju
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorAbir Das
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorRajib Mandal
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorHarihara Subramanian Ravi Sankar
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorDr. Subramani Kumaran
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorDr. J. Richard Premkumar
PG & Research Department of Chemistry, Bishop Heber College, 620017 Tiruchirappalli, Tamil Nadu, India
Search for more papers by this authorDipanti Borah
Department of Chemistry, Indian Institute of Technology Bombay, Powai, 400076 Mumbai, Maharashtra, India
Search for more papers by this authorCorresponding Author
Prof. Dr. Basker Sundararaju
Department of Chemistry, Indian Institution of Technology Kanpur, 208016 Kanpur, Uttar Pradesh, India
Search for more papers by this authorA previous version of this manuscript has been deposited on a preprint server (https://doi.org/10.26434/chemrxiv-2023-1rqz1).
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.
Conflict of interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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