Anthony J. Pearson

Rudolph and Susan Rense Professor of Chemistry

pearson_cas2009_300pxInterests

Organic Chemistry, Organometallic Chemistry, Catalysis, Natural Products, Synthesis

Education and Awards

  • BSc, University of Leeds (UK) 1971
  • PhD, University of Aston (UK) 1974
  • Postdoctoral Fellow, Australian National University, 1974-77
  • Sir Gilbert Morgan Medal, Society for Chemical Industry, UK, 1973
  • SERC Advanced Fellow, Cambridge University (UK), 1977-82
  • CWRU Sigma XI Research Award, 1984
  • John S. Diekhoff Award for disginguished graduate teaching, 1994

Research Synopsis

We currently have two research themes: (1) Development of organoiron chemistry for applications in organic synthesis, and (2) Development of organocatalysts for asymmetric aldol reactions.

The discovery and development of new reactions is a very exciting outcome in organic synthesis research. Our group has been fortunate to discover a number of new reactions (all by accident!), some of which are illustrated here.

Verrucarol

This [6+2] ene-type reaction was discovered by graduate student Mark Zettler, the example given here showing how a densely substituted multicyclic structure can be constructed, that relates to the sesquiterpenoid verrucarol. Subsequent work by graduate student Xiaolong Wang resulted in a two-step procedure for stereospecific conversion of a readily prepared cyclohexadiene into a molecule that has much of the structure in place for synthetic approaches to the complex alkaloid gelsemine. Xiaolong also developed a sereocontrolled asymmetric ene cyclization that uses dynamic diastereoselectivity during the ene coupling process:

Gelsemine

Recent work on this ene reaction has shown that the pendant alkene can be replaced by an aldehyde, which could provide an approach to compounds such as spirostaphylotrichin A:

SpirostaphylotrichinA

Organocatalyzed Asymmetric Aldol Reactions

We have recently developed several new proline-derived organocatalysts for use in asymmetric aldol reactions. The design principle uses an anthranilic acid core as a structural template to induce a reverse turn and give a chiral binding pocket for the substrates, as exemplified here:

boxed_structurePearsonPanda2011

Selected Publications

  1. A. J. Pearson and S. Cui. Ruthenium Mediated SNAr Reactions in Synthetic Approaches to Ristocetin A Aglycon: Preparation of an ABCD Ring Intermediate. Tetrahedron Lett. 200546, 2639-2642.
  2. A. J. Pearson and Y. Kwak. A New Method for Stereoselective Oxidation of Chiral 2-Pyrrolidino-1-ethanol Derivatives to Oxazolopyrrolidines Using Trimethylamine-N-oxide in the Presence of Iron Carbonyls. Tetrahedron Lett. 200546, 3407-3410.
  3. A. J. Pearson and X. Wang. Dynamic Kinetic Resolution During Iron Carbonyl Promoted [6+2] Ene-type Reactions. Tetrahedron Lett.200546, 3123-3126.
  4. A. J. Pearson and Y. Kwak. A New Method for Selective Oxidation of Allylic and Benzylic Alcohols. Tetrahedron Lett.  200546, 5417-5419.
  5. A. J. Pearson and X. Wang. A Stereospecific Intramolecular [4π+4π] Cycloaddition Reaction Between Tricarbonyliron-complexed Cyclohexadiene and Pendant Dienes. Tetrahedron Lett. 200546, 4809-4811.
  6. A. J. Pearson and M. Zhang. Hydroxyl-Directed Conjugate Additions of Carbon Nucleophiles to Cyclopentadienones. Organic Lett.20068, 3267-3269.
  7. A. J. Pearson, J. D. Protasiewicz, J. Updegraff, and M. Zhang. Stereoselective Conjugate Additions of Grignard Reagents to Cyclopentadienones. Tetrahedron Lett. 200748, 5569-5572.
  8. A. J. Pearson, H. Sun and X. Wang. Dynamic Diastereoselectivity During Iron Carbonyl Mediated Spirocyclization Reactions. J. Org. Chem. 200772, 2547-2557.
  9. A. J. Pearson and H. Sun. Cyclohexadieneiron Tricarbonyl. Electronic Encyclopedia of Reagents for Organic Synthesis. L. A. Paquette, Editor-in-Chief. John Wiley & Sons, Chichester, 2007.
  10. A. J. Pearson and H. Sun. An Iron Promoted Aldehyde-Diene Cyclocoupling Reaction. J. Org. Chem. 200772, 7693-7700.
  11. A. J. Pearson and D. V. Ciurea. Synthesis of a Key Precursor for Orienticin C and Model Study on Ruthenium-mediated Macrocyclization. J. Org. Chem. 200873, 760-763.
  12. H. Paramahamsan, A. J. Pearson, A. A. Pinkerton, and E. A. Zhurova. Toward an Understanding of 1,5 Asymmetric Induction During Nucleophile Addition to Arenechromium Tricarbonyl Complexes: Conformational Preference and Orientation of the Chromium Tricarbonyl Tripod for Transmission of Chirality. Organometallics 200827, 900-907.
  13. A. J. Pearson, D. V. Ciurea, and A. Velankar. Studies Toward the Total Synthesis of Ristocetin A Aglycone Using Arene-Ruthenium Complexes as SNAr Substrates: Construction of an Advanced Tricyclic Intermediate. Tetrahedron Lett. 200849¸ 1922-1926.
  14. H. Pramahamsan, A. J. Pearson, N. M. Pinkerton and A. A. Pinkerton. 1,5-Asymmetric Induction During Nucleophile Additions to Arenechromium Tricarbonyl Complexes, η6-{4-[[Spiro[(1R,2S)-1,7,7-trimethylbicyclo[2.2.1]heptane-3.2′-[1,3-dioxolan]-2-yl]oxy]toluene}chromium Tricarbonyl. Acta Cryst. 2008C64, m147-m148.
  15. A. J. Pearson and Y. Zhou. Diels-Alder Reactions of Cyclopentadienones with Aryl Alkynes To Form Biaryl Compounds. J. Org. Chem.200974, 4242-4245.
  16. A. J. Pearson, E. Kim, and H. Sun. A Synthetic Pathway To Diquinane and Angular Triquinane Systems via an Iron Carbonyl Promoted Tandem [6+2] Ene Type Reaction. Tetrahedron 201066, 4943-4946.
  17. A. J. Pearson and S. Panda. N-Prolinylanthranilic Acid Derivatives as Bifunctional Organocatalysts for Asymmetric Aldol Reactions.Tetrahedron 201167, 3969-3975.
  18. A. J. Pearson and S. Panda. N-Prolinylanthranilamide Pseudopeptides as Bifunctional Organocatalysts for Asymmetric Aldol Reactions. Org. Lett. 201113, 5548-5551.

Textbook and Monograph Publications

  • A. J. Pearson  Metallo-Organic Chemistry, John Wiley & Sons 1985, 388 pp.
  • A. J. Pearson  Iron Compounds in Organic Synthesis, Academic Press, 1994.
  • Encyclopedia of Reagents for Organic Synthesis. L. A. Paquette, Editor-in-Chief. S. D. Burke, R. M. Coates, R. L. Danheiser, S. E. Denmark, D. J. Hart, L. S. Liebeskind, D. C. Liotta, A. J. Pearson, H. J. Reich, J. H. Rigby, and W. R. Roush, Editors. John Wiley & Sons, Chichester, 1995.
  • Handbook of Reagents for Organic Synthesis.  L. A. Paquette, Editor-in-Chief. Volume C, Activating Agents and Protecting Groups. A. J. Pearson and W. R. Roush, Editors. John Wiley and Sons, Chichester, 1999.

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Contact

ajp4@case.edu
216.368.5920
Millis 433A