Professor of Chemistry
Merkert Center 318
Telephone: 617-552-1483
Email: peter.zhang@bc.edu
ORCID 0000-0001-7574-8409
Development of fundamentally new catalytic systems for stereoselective chemical transformations and their applications for practical synthesis of organic molecules.
Our research program focuses on the development of fundamentally new catalytic systems for stereoselective chemical transformations and their applications in practical organic synthesis. We are particularly interested in metalloradical catalysis (MRC), a concept that employs open-shell transition-metal complexes as one-electron catalysts to generate and control reactive organic radicals. Our studies have established structurally well-defined Co(II) porphyrin complexes, including D₂-symmetric chiral amidoporphyrins, as effective metalloradical catalysts for a broad range of stereoselective radical transformations. These reactions proceed through metal-entangled organic radicals, such as α-Co(III)-alkyl and α-Co(III)-aminyl radicals, enabling new approaches to cyclopropanation, C–H functionalization, cyclization, and related bond-forming processes. More recently, we have expanded MRC to Fe(III)-based systems, including the development of catalytic radical processes involving α-Fe(IV)-alkyl and α-Fe(IV)-aminyl radical intermediates for cyclopropanation and C–H amination. Through the design of new open-shell catalysts and mechanistic understanding of their radical intermediates, we seek to address long-standing challenges in reactivity, chemoselectivity, and stereoselectivity in organic synthesis.
· Lee, W.-C. C.; Zhang, X. P. “Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions” Angew. Chem. Int. Ed. 2024, 63, e202320243. [Link]
· Xu, P.; Wang, D.-S.; Zhu, Z.-Y.; Zhang, X. P. “Enantioselective Radical Dearomative Conjugate Amination Enabled by Co(II)-Based Metalloradical Catalysis” Nat. Catal. 2025, 8, 1051–1061. [Link]
· Lee, W.-C. C.; Wang, D.-S.; Zhu, Y.-L.; Zhang, X. P. “Iron(III)-Based Metalloradical Catalysis for Asymmetric Cyclopropanation via Stepwise Radical Mechanism” Nat. Chem. 2023, 15, 1569–1580. [Link]
· Xu, P.; Xie, J.-J.; Wang, D.-S.; Zhang, X. P. “Metalloradical Approach for Concurrent Control in Intermolecular Radical Allylic C−H Amination” Nat. Chem. 2023, 15, 498–507. [Link]
· Lang, K.; Hu, Y.; Lee, W.-C. C.; Zhang, X. P. “Combined Radical and Ionic Approach for The Enantioselective Synthesis of b-Functionalized Amines from Alcohols” Nat. Synth. 2022, 1, 548–557. [Link]