Chemistry Department Faculty
X. Peter Zhang
Professor of Chemistry
X. Peter Zhang
Ph.D.
Contact
Merkert Center 318
Telephone: 617-552-1483
Email: peter.zhang@bc.edu
ORCID 0000-0001-7574-8409
Education
- Ph.D., University of Pennsylvania
Research Interests
Development of fundamentally new catalytic systems for stereoselective chemical transformations and their applications for practical synthesis of organic molecules.
Research
Our research program has centered on the development of fundamentally new catalytic systems for stereoselective chemical transformations and their applications for practical synthesis of organic molecules. We are particularly interested in developing one-electron catalytic approaches for homolytic radical chemistry to harness the vast potential of radical reactions for stereoselective construction of molecular structures. To this end, we have formulated “Metalloradical Catalysis” (MRC) as a concept to guide the development of general approaches for controlling reactivity and selectivity of various radical processes. For achieving enantioselective radical reactions, we have developed a family of unique chiral metalloradical catalysts based on structurally well-defined Co(II) complexes of D2-symmetric chiral porphyrins with tunable electronic, steric, and chiral environments. These Co(II)-based metalloradical catalysts have shown to be highly effective for a wide range of stereoselective organic reactions. Due to their distinctive radical mechanisms that involve unprecedented metal-stabilized radical intermediates, such as α-metalloalkyl radicals (also known as metallocarbene radicals) and ɑ-metalloaminyl radicals (also known as metallonitrene radicals), the Co(II)-based metalloradical systems enable addressing some long-standing challenges in these important organic transformations.
Selected Honors and Awards
- NSF CAREER Award, 2006
- ORAU Ralph Powe Faculty Award, 2003
- NIH Postdoctoral Fellowship, 1996
Representative Key Publications
- Xie, J.-J.; Xu, P.; Zhu, Y.-L.; Wang, J.-Y.; Lee, W.-C. C.; Zhang, X. P. “New Catalytic Radical Process Involving 1,4-Hydrogen Atom Abstraction: Asymmetric Construction of Cyclobutanones” J. Am. Chem. Soc. 2021, 143, 111670–111678. [Link]
- Wang, X.-X.; Ke, J.; Zhu, Y.-L.; Deb, A.; Xu, Y.-J.; Zhang, X. P. “Asymmetric Radical Process for General Synthesis of Chiral Heteroaryl Cyclopropanes” J. Am. Chem. Soc. 2021, 143, 11121–11129. [Link]
- Zhang, C.-Z.; Wang, D.-S.; Lee, W.-C. C.; McKillop, A. M.; Zhang, X. P. “Controlling Enantioselectivity and Diastereoselectivity in Radical Cascade Cyclization for Construction of Bicyclic Structures” J. Am. Chem. Soc. 2021, 143, 11130–11140. [Link]
- Lee, W.-C. C.; Wang, D.-S.; Zhang, C.-Z.; Xie, J.-J.; Li, B.; Zhang, X. P. “Asymmetric Radical Cyclopropanation of Dehydroaminocarboxylates: Stereoselective Synthesis of Cyclopropyl a-Amino Acids” Chem 2021, 7, 1588–1601. [Link]
- Riart-Ferrer, X.; Sang, P.; Tao, J.-R.; Xu, H.; Jin, L.-M.; Lu, H.-J.; Cui, X.; Wojtas, L.; Zhang, X. P. “Metalloradical Activation of Carbonyl Azides for Enantioselective Radical Aziridination” Chem 2021, 7, 1120–1134. [Link]
- Lang, K.; Li, C.-Q.; Kim, I.; Zhang, X. P. “Enantioconvergent Amination of Racemic Tertiary C-H Bonds” J. Am. Chem. Soc. 2020, 142, 20902–20911. [Link]
- Jin, L.-M.; Xu, P.; Xie, J.-J.; Zhang, X. P. “Enantioselective Intermolecular Radical C−H Amination” J. Am. Chem. Soc. 2020, 142, 20828–20836. [Link]
- Hu, Y.; Lang, K.; Li, C.-Q.; Gill; J. B.; Kim, I.; Lu, H.-J.; Fields, K. B.; Marshall, M. K.; Cheng, Q.-G.; Cui, X.; Wojtas, L.; Zhang, X. P. “Enantioselective Radical Construction of 5-Membered Cyclic Sulfonamides by Metalloradical C−H Amination” J. Am. Chem. Soc. 2019, doi.org/10.1021/jacs.9b08894.
- Lang, K.; Torker, S.; Wojtas, L.; Zhang, X. P. “Asymmetric Induction and Enantiodivergence in Catalytic Radical C–H Amination via Enantiodifferentiative H-Atom Abstraction and Stereoretentive Radical Substitution” J. Am. Chem. Soc. 2019, 141, 12388–12396. [Link]
- Hu, Y.; Lang, K.; Tao, J.-R.; Marshall, M. K.; Cheng, Q.-G.; Cui, X.; Wojtas, L.; Zhang, X. P. “Next-Generation D2-Symmetric Chiral Porphyrins for Cobalt(II)-Based Metalloradical Catalysis: Catalyst Engineering by Distal Bridging” Angew. Chem. Int. Ed. 2019, 58, 2670–2674. [Link]
- Li, C.-Q.; Lang, K.; Lu, H.-J.; Hu, Y.; Cui, X.; Wojtas, L.; Zhang, X. P. “Catalytic Radical Process for Enantioselective Amination of C(sp3)–H Bonds” Angew. Chem. Int. Ed. 2018, 57, 16837–16841. [Link]
- Wang, Y.; Wen, X.; Cui, X.; Zhang, X. P. “Enantioselective Radical Cyclization for Construction of 5-Membered Ring Structures by Metalloradical C–H Alkylation” J. Am. Chem. Soc. 2018, 140, 4792–4796. [Link]
- Jiang, H.-L.; Lang, K.; Lu, H.-J.; Wojtas, L.; Zhang, X. P. “Asymmetric Radical Bicyclization of Allyl Azidoformates via Cobalt(II)-Based Metalloradical Catalysis” J. Am. Chem. Soc. 2017, 139, 9164–9167. [Link]
- Wang, Y.; Wen, X.; Cui, X.; Wojtas, L.; Zhang, X. P. "Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis" J. Am. Chem. Soc. 2017, 139, 1049–1052. [Link]