Experimental and computational studies establish the operation of Fe(iii)-based metalloradical catalysis for the asymmetric cyclopropanation of alkenes with different classes of diazo compounds. The reaction proceeds through a stepwise radical mechanism involving α-Fe(iv)-alkyl and γ-Fe(iv)-alkyl radical intermediates. This work provides a future direction for the development of metalloradical catalysis.
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Wang, X. & Zhang, X. P. in Transition Metal-Catalyzed Carbene Transformations (eds Wang, J., Che, C.-H. & Doyle, M. P.) 25–66 (Wiley, 2022). A book chapter that presents the development of Co(ii)-based MRC and related applications for selective carbene transfers.
Lee, W.-C. C. & Zhang, X. P. Asymmetric radical cyclopropanation of alkenes. Trends Chem. 4, 850–851 (2022). An article that highlights the general stepwise radical mechanism for asymmetric olefin cyclopropanation through Co(ii)-based MRC.
Xie, J. et al. New catalytic radical process involving 1,4-hydrogen atom abstraction: asymmetric construction of cyclobutanones. J. Am. Chem. Soc. 143, 11670–11678 (2021). A paper that reports the application of Co(ii)-based MRC for asymmetric radical 1,4-C–H alkylation to construct cyclobutanones.
Xu, P., Xie, J., Wang, D.-S. & Zhang, X. P. Metalloradical approach for concurrent control in intermolecular radical allylic C–H amination. Nat. Chem. 15, 498–507 (2023). A paper that reports the application of Co(ii)-based MRC for controlling multiple selectivities in allylic radical C–H amination.
Das, S. K., Roy, S., Khatua, H. & Chattopadhyay, B. Iron-catalyzed amination of strong aliphatic C(sp3)–H bonds. J. Am. Chem. Soc. 142, 16211–16217 (2020). A paper that presents Fe(ii)-based MRC for radical 1,5- and 1,6-C–H amination of 1,2,3,4-tetrazoles to construct N-heterocycles.
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This is a summary of: Lee, W.-C. C. et al. Iron(iii)-based metalloradical catalysis for asymmetric cyclopropanation via a stepwise radical mechanism. Nat. Chem. https://doi.org/10.1038/s41557-023-01317-8 (2023).
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Iron(iii) porphyrin complexes as metalloradical catalysts. Nat. Chem. 15, 1499–1500 (2023). https://doi.org/10.1038/s41557-023-01318-7