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Peter  Zhang

Peter Zhang

Peter Zhang
Professor

Contact

Office: BSF 310
Phone: 813-974-7249
Email:

Links

Education

Ph.D., University of Pennsylvania
Postdoctoral Fellow, Massachusetts Institute of Technology

Research

Metalloradical Catalysis (MRC) for Stereoselective Organic Synthesis

Metalloporphyrins

One of the major efforts of our research program has centered on the development of efficient catalytic systems for stereoselective chemical transformations and their applications in practical synthesis of organic molecules with biological and pharmaceutical interests. We are particularly interested in developing 1e catalytic approaches to harness the vast potential of radical reactions for stereoselective construction of molecular structures. To this end, we have been in the process of establishing metalloradical catalysis (MRC) as a new concept 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 been shown to be highly effective for a wide range of stereoselective carbene and nitrene transfer reactions, including alkene cyclopropanation, alkene aziridination, C–H alkylation and C–H amination. Due to their distinctive radical mechanisms that involve unprecedented metallocarbene and metallonitrene radical intermediates, the Co(II)-based metalloradical systems enable addressing some long-standing challenges in these important organic transformations. A related active effort has been the pursuit toward heterogenizing these homogeneous catalytic systems via construction of metal-porphyrin frameworks (MPFs).

Current Funding

View our currently funded projects here.

Research Assistant Professor

Dr. Xin Cui

Postdoctoral Associates

Dr. Yang Hu, Dr. Limei Jin, Dr. Kai Lang, Dr. Chaoqun Li and Dr. Xue Xu

Undergraduate Students

Jennifer Le, Nicholas Raymond, Thiago Arzua and McKenzie Marshall

Graduate Students

Qigan Cheng, Yuan Cui, Joseph Gill, Sean Johnson, Christopher Lizardi, Lucas Parvin, Jingyi Wang, Yong Wang, Xin Wen

Current Courses

RefCourseSecCourse TitleCRDayTimeLocation
24500IDS 4914047Adv Undergrad Research Exp
0
TBA TBA
12581CHM 4932006Organometallic Chemistry
Pre-requisite: CHM 2210 and CHM 2211
3TR5:00pm-6:15pm
NES 103
17593CHM 4970034Undergraduate Research
Requires Instructor Approval; S-U Only
1-3
TBA TBA
10149CHM 6938003Organometallic Chemistry
3TR5:00pm-6:15pm
NES 103
23494CHM 6971034Thesis: Master's
S-U Only
2-19
TBA TBA
23497CHM 6973034Directed Research
S-U Only
1-19
TBA TBA
23500CHM 7820034Directed Research
S-U Only
1-19
TBA TBA
23503CHM 7980034Dissertation: Doctoral
Adm To Doc Candidacy Req S-U Only
2-19
TBA TBA

Recent Publications

  1. Xu, X.; Zhu, S.-F.; Cui, X.; Wojtas, L.; Zhang, X. P. “Cobalt(II)-Catalyzed Asymmetric Olefin Cyclopropanation with α-Ketodiazoacetates and Iodide-Promoted Stereospecific Epimerization of Resulting (E)-1,1-Cyclopropaneketoesters” Angew. Chem. Int. Ed. 2013, DOI: 10.1002/anie.201305883. [Link]
  2. Jin, L.-M.; Xu, X.; Lu, H.; Cui, X.; Wojtas, L.; Zhang, X. P. “Effective Synthesis of Chiral N-Fluoroaryl Aziridines via Enantioselective Aziridination of Alkenes with Fluoroaryl Azides” Angew. Chem. Int. Ed. 2013, 52, 5309–5313. [Link]
  3. Cui, X.; Xu, X.; Wojtas, L.; Kim, M. M.; Zhang, X. P. “Regioselective Synthesis of Multisubstituted Furans via Metalloradical Cyclization of Alkynes with α-Diazocarbonyls: Construction of Functionalized α-Oligofurans” J. Am. Chem. Soc. 2012, 134, 19981–19984. [Link]
  4. Meng, L.; Cheng, Q.; Kim, C.-S.; Gao, W.-Y.; Wojtas, L.; Chen, Y.-S.; Zaworotko, M. J.; Zhang, X. P.; Ma, S.-Q. “Crystal Engineering of a Microporous, Catalytically Active fcu Topology MOF Using a Custom-Designed Metalloporphyrin Linker” Angew. Chem. Int. Ed. 2012,51, 10082–10085. [Link]
  5. Lu, H.-J.; Jiang, H.-L.; Hu, Y.; Wojtas, L.; Zhang, X. P. “Stereoselective Radical Amination of Electron-Deficient C–H Bonds by Co(II)-Based Metalloradical Catalysis: Synthesis of alpha-Amino Acid Derivatives via alpha-C–H Amination of Esters and Amides” Org. Lett. 2012, 14, 5158–5161. [Link]
  6. Xu, X.; Lu, H.-J.; Ruppel, J. V.; Cui, X.; de Mesa, S. L.; Wojtas, L.; Zhang, X. P. “Highly Asymmetric Intramolecular Cyclopropanation of Acceptor-Substituted Diazoacetates by Co(II)-Based Metalloradical Catalysis: Iterative Approach for Development of New Generation Catalysts” J. Am. Chem. Soc. 2011, 133, 15292-15295. [Link]
  7. Lyaskovskyy, V.; Suarez, A. I. O.; Lu, H.-J.; Zhang, X. P.; de Bruin, B. “Mechanism of Cobalt(II) Porphyrin-Catalyzed C–H Amination with Organic Azides: Radical Nature and H-Atom Abstraction Ability of Cobalt(III)-Nitrene Key Intermediates” J. Am. Chem. Soc. 2011, 133, 12264-12273. [Link]
  8. Lu, H.-J.; Dzik, W. I.; Xu, X.; Wojtas, L.; de Bruin, B.; Zhang, X. P. “Experimental Evidence for Cobalt(III)-Carbene Radicals: Key Intermediates in Cobalt(II)-Based Metalloradical Cyclopropanation” J. Am. Chem. Soc. 2011, 133, 8518-8521. [Link]
  9. Cui, X.; Xu, X.; Lu, H.-J.; Zhu, S.-F.; Wojtas, L.; Zhang, X. P. "Enantioselective Cyclopropenation of Alkynes with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis" J. Am. Chem. Soc. 2011, 133, 3304-3307. [Link]
  10. Wang, X.-S.; Meng, L.; Cheng, Q.-G.; Kim, C.-S.; Wojtas, L.; Chrzanowski, M.; Chen, Y.-S.; Zhang, X. P.; Ma, S.-Q. "A Three-Dimensional Porous Metal-Metalloporphyrin Framework Consisting of Nanoscopic Polyhedral Cages with a High Density of Open Metal Sites" J. Am. Chem. Soc. 2011, 133, 16322-16325. [Link]
  11. Lu, H.-J.; Jiang, H.-L.; Hu, Y.; Wojtas, L.; Zhang, X. P. "Chemoselective Intramolecular Allylic C-H Amination over C=C Aziridination through Co(II)-Based Metalloradical Catalysis" Chem. Sci. 2011, 2, 2361-2366. [Link]
  12. Lu, H.-J.; Zhang, X. P. "Catalytic C–H Functionalization by Metalloporphyrins: Recent Developments and Future Directions" Chem. Soc. Rev. 2011, 40, 1899-1909. [Link]
  13. Lu, H.-J.; Jiang, H.-L.; Wojtas, L.; Zhang, X. P. "Selective Intramolecular C–H Amination via Metalloradical Activation of Azides: Synthesis of 1,3-Diamines under Neutral and Nonoxidative Conditions" Angew. Chem. Int. Ed. 2010, 49, 10192–10196. [Link]
  14. Zhu, S.-F.; Xu, X.; Perman, J. A.; Zhang, X. P. "A General and Efficient Cobalt(II)-Based Catalytic System for Highly Stereoselective Cyclopropanation of Alkenes with α-Cyano-Diazoacetates" J. Am. Chem. Soc. 2010, 132, 12796–12799. [Link]
  15. Dzik, W. I.; Xu, X.; Zhang, X. P.; Reek, J. N. H.; de Bruin, B. "Carbene Radicals' in CoII(por)-Catalyzed Olefin Cyclopropanation" J. Am. Chem. Soc. 2010, 132, 10891–10902. [Link]
  16. Lu, H.-J.; Tao, J.-R.; Jones, J. E.; Wojtas, L.; Zhang, X. P. "Co(II)-Catalyzed Intramolecular C–H Amination of Phosphoryl Azides: Formation of 6- and 7-Membered Cyclophosphoramidates" Org. Lett. 2010, 12, 1248–1251. [Link]
  17. Subbarayan, V.; Ruppel, J. V.; Zhu, S.-F.; Perman, J. A.; Zhang, X. P. "Highly Asymmetric Cobalt-Catalyzed Aziridination of Alkenes with Trichloroethoxysulfonyl Azide (TcesN3)" Chem. Commun. 2009, 4266–4268. [Link]
  18. Ruppel, J. V.; Gauthier, T. J.; Snyder, N. L.; Perman, J. A.; Zhang, X. P. "Asymmetric Cobalt-Catalyzed Cyclopropanation with Succinimidyl Diazoacetate: General Synthesis of Optically Active Cyclopropyl Carboxamides" Org. Lett. 2009, 11, 2273-2276. [Link]
  19. Zhu, S.-F.; Perman, J. A.; Zhang, X. P. "Acceptor/Acceptor-Substituted Diazo Reagents for Carbene Transfers: Cobalt-Catalyzed Asymmetric (Z)-Cyclopropanation of Alkenes with α-Nitro-Diazoacetates" Angew. Chem. Int. Ed. 2008, 47, 8460–8463. [Link]
  20. Zhu, S.; Ruppel, J. V.; Lu, H.; Wojtas, L.; Zhang, X. P. "Cobalt-Catalyzed Asymmetric Cyclopropanation with Diazosulfones: Rigidification and Polarization of Ligand Chiral Environment via Hydrogen Bonding and Cyclization" J. Am. Chem. Soc. 2008, 130, 5042–5043. [Link]
  21. Ruppel, J. V.; Jones, J. E.; Huff, C. A.; Kamble, R. M.; Chen, Y.; Zhang, X. P. "A Highly Effective Cobalt Catalyst for Olefin Aziridination with Azides: Hydrogen Bonding-Guided Catalyst Design" Org. Lett. 2008, 10, 1995-1998. [Link]
  22. Chen, Y.; Ruppel, J. V.; Zhang, X. P. "Cobalt-Catalyzed Asymmetric Cyclopropanation of Electron-Deficient Olefins" J. Am. Chem. Soc. 2007, 129, 12074–12075. [Link]
  23. Ruppel, J. V.; Kamble, R. M.; Zhang, X. P. "Cobalt-Catalyzed Intramolecular C-H Amination with Arylsulfonyl Azides" Org. Lett. 2007, 9, 4889-4892. [Link]
  24. Baskaran, D.; Mays, J. W.; Zhang, X. P.; Bratcher, M. S. "Carbon Nanotubes with Covalently Linked Porphyrin Antennae: Photoinduced Electron Transfer" J. Am. Chem. Soc. 2005, 127, 6916–6917. [Link]
  25. Chen, Y.; Fields, K. B.; Zhang, X. P. "Bromoporphyrins as Versatile Synthons for Modular Construction of Chiral Porphyrins: Cobalt-Catalyzed Highly Enantioselective and Diastereoselective Cyclopropanation" J. Am. Chem. Soc. 2004, 126, 14718–14719. [Link]