The Origin of Enantioselectivity of Aryl Terminal Alkenes Hydroboration Catalyzed by Cobalt Complex: A Density Functional Theory (DFT) Study
Density functional theory (DFT) studies reveal the origin of the regioselectivity and stereoselectivity in Co-IPO-catalyzed hydroboration of aryl alkenes. Four insertion pathways dictate selectivity, with <i>anti</i>-Markovnikov <i>S</i>-product formation (Path A) being energetically favored. The alkene insertion step and σ-bond metathesis step jointly determine the selectivity of the reaction. In addition, the steric hindrance from the -NPh<sup><i>i</i></sup>Pr<sub>2</sub> moiety of the IPO ligand critically controls selectivity. Interestingly, substituting -NPh<sup><i>i</i></sup>Pr<sub>2</sub> with -NCH<sub>3</sub> shifts selectivity toward Markovnikov products.
Authors
- Ming Lei (ORCID: https://orcid.org/0000-0001-5765-9664)
- Ling Zhu
- Min Pu (ORCID: https://orcid.org/0000-0001-5212-728X)
- Zuoyin Yang
- Xiaofan Shi (ORCID: https://orcid.org/0000-0002-7587-4971)
- Lin Zhang (ORCID: https://orcid.org/0000-0003-3825-4973)
Institutions
- University of Science and Technology of China (CN)
- Xiamen University (CN)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- Microscale (United States) (US)
- Beijing University of Chemical Technology (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-04-08
- DOI
- https://doi.org/10.1021/acs.orglett.5c00809
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Beijing Municipal Natural Science Foundation