Professor of Chemistry
Ph. D., The Ohio State University, 1997
jeffrey.n.johnston@vanderbilt.edu
The Johnston Group

Our programs are tied by the common theme of organic synthesis, but can be expressed to reasonably diverse endpoints. Specifically, we are interested in the development of new reactions and reagents for natural product total synthesis, and in recent years have contributed a variety of new reactions to the chemist's arsenal: free radical-mediated aryl and vinyl amination, a Brønsted acid-catalyzed aza-Darzens, and a new acid catalyzed olefin aminoacyloxylation reaction, among others. We are now applying these reactions to the targets that inspired them. For example, our synthesis of mitomycin C uses the acid-catalyzed aza-Darzens reaction, in addition to a regioselective enamine-quinone coupling. As a result, we are able to synthesize an advanced intermediate with considerable brevity. An emerging area within our program is the use of indoline 'a-amino acids' made uniquely by our amination technology - for applications in bioorganic chemistry.

We have also advanced the concept and first embodiment of chiral proton catalysis. Reagents known as BAM-protic acid complexes are bifunctional, containing both a polar ionic hydrogen bond (a Brønsted acid) and a Brønsted base. These catalysts synchronize the activation of two substrates while orienting the electrophile for stereoselective addition. The net result is the ability to make a variety of products in enantioenriched form through carbon-carbon bond-forming reactions. From this perspective, these catalysts function in a chemically similar manner to enzymes. An underlying goal of our program is to understand how biological catalysts achieve substrate activation, and determine how this can be translated to small molecule catalysts.

Finally, we have ongoing internal and collaborative projects in organometallic catalysis that target reactions not amenable to protic acid catalysis. Our contributions in this area include the development of the first axially chiral b-diketiminate (IAN amines), and the study of their coordination chemistry with group IV metals.

Through these studies, the student is trained how to think about problems in organic chemistry from an approach that involves extensive laboratory experimentation. Germane to this training is the routine use of spectroscopic (NMR, IR, mass spectroscopy, X-ray diffraction) and analytical (chiral stationary phase HPLC) techniques.

Selected Publications

Chandra, A.; Pigza, J. A.; Han, J.-S.; Mutnick, D. M.; Johnston, J. N. Total Synthesis of the Lycopodium Alkaloid (+)-Serratezomine A. Journal of the Amercian Chemical Society. 2009, 131: 3470-3471.

Donahue, M. G.; Hong, K. B.; Johnston, J. N. Comparison of Triazolinium Triflate Fragmentation Rates as a Tool to Assay Relative Competency of Brønsted Bases in Proton Tranfer. Bioorganic and Medicianl Chemistry Letters. 2009, 19: 4971-4973.

Troyer, T. L.; Muchalski, H.; Johnston, J. N. A Brønsted Acid Catalyzed syn-Selective Glycolate Mannich Reaction. Chemical Communications. 2009, in press

Hong K.B.; Donahue M.G.;, Johnston J.N. On the nature of rate acceleration in the synthesis and fragmentation of triazolines by Bronsted acid: Secondary catalysis by water (hydronium triflate). Journal of the American Chemical Society. 2008, 130 (7): 2323-2328.

Shen B.; Johnston J.N. A Formal Enantioselective Acetate Mannich Reaction: The Nitro Functional Group as a Traceless Agent for Activation and Enantiocontrol in the Synthesis of beta-Amino Acids. Organic Letters. 2008, 10 (20): 4397-4400.

Wilt, J. C.; Pink, M.; Johnston, J. N. A Diastereo- and Enantiselective Synthesis of -Substituted anti-a,β-Diaminophosphonic Acid Derivatives. Chemical Communications. 2008, 35: 4177-4179.

Viswanathan, R.; Smith, C. R.; Prabhakaran, E. N.; Johnston, J. N. Free Radical-Mediated Aryl Amination: Convergent Two- and Three-Component Couplings to Chiral 2,3-Disubstituted Indolines. Journal of Organic Chemistry. 2008, 73: 3040-3046.

Singh, A.; Johnston, J. N. A Diastereo- and Enantioselective Synthesis of α-Substituted syn-α,β-Diamino Acids. Journal of the Amercian Chemical Society. 2008, 130: 5866-5867.

Luesse, S. B.; Counceller, C. M.; Wilt, J. C.; Perkins, B. R.; Johnston, J. N. A Preparation of Enantiomerically Enriched Axially Chiral β-Diketimines: Synthesis of (-)- and (+)-IAN Amine. Organic Letters. 2008, 10: 2445-2447.

Chandra A.; Viswanathan R.; Johnston J. N. Synthesis of the ABC- and D-ring systems of the indole alkaloid ambiguine G. Organic Letters. 2007, 9: 5027-5029.

Singh, A. S.; Yoder, R. A.; Shen, B. S.; Johnston, J. N. Chiral Proton Catalysis: Enantioselective Brφnsted Acid Catalyzed Additions of Nitroacetic Acid Derivatives as Glycine Equivalents. Journal of the Amercian Chemical Society. 2007, 129: 3466-3467.

Williams, A. L.; Srinivasan, J. M.; Johnston, J. N. Synthesis of an Advanced Intermediate En Route to the Mitomycin Natural Products. Organic Letters. 2006, 8: 6047-6049.

Hess, A. S.; Yoder, R. A.; Johnston, J. N. Chiral Proton Catalysis: pK_a Determination for a BAM-HX Brφnsted Acid. Synlett. 2006, 1: 147.

Donahue, M. G.; Johnston, J. N. Preparation of a Protected Phosphoramidon Precursor via an H-Phosphonate Coupling Strategy. Bioorganic and Medicianl Chemistry Letters. 2006, 16: 5602.

Srinivasan, J. M.; Burks, H. E.; Smith, C. R.; Viswanathan, R.; Johnston, J. N. Free Radical-Mediated Aryl Amination: A Practical Synthesis of (R)- and (S)-7-Azaindoline a-Amino Acid. Synthesis Practical Synthetic Procedures. 2005: 330-333.

Mahoney, J. M.; Smith, C. R.; Johnston, J. N. Brφnsted Acid-Promoted Olefin Aziridination and Formal anti-Aminohydroxylation. Journal of the Amercian Chemical Society. 2005, 127: 1354-1355.

Yoder, R. A.; Johnston, J. N. A Case Study in Biomimetic Total Synthesis: Polyolefin Carbocyclizations to Terpenes and Steroids. Chemical Review. 2005, 105: 730.

S. B.; Yoder, R. A.; Johnston, J. N. Enantioenriched Axially Chiral b-Diketimines: Determination of the IAN-Amine Barrier to Atropisomerization. Heterocycles. 2004, 62: 223-227.

Williams, A. L.; Johnston, J. N. The Brφnsted Acid-Catalyzed Direct Aza-Darzens Synthesis of N-Alkyl cis-Aziridines. Journal of the Amercian Chemical Society. 2004, 126: 1612-1613.

Nugent, B. M.; Yoder, R. A.; Johnston, J. N. Chiral Proton Catalysis: A Catalytic Enantioselective Direct Aza-Henry Reaction. Journal of the Amercian Chemical Society. 2004, 126: 3418-3419.

S. B.; Huffman, J. C.; Yoder, R. A.; Coalter, J. N. III; Johnston, J. N. IAN-Amines: Chiral C₂-Symmetric Zirconium(IV) Complexes from Readily Modified Axially Chiral C₁-Symmetric b-Diketimines. Organometallics. 2004, 23: 2238-2250.

S. B.; Coalter, J. N. III; Pink, M.; Johnston, J. N. A Remarkably Facile Zirconium(IV) to Aluminum(III) b-Diketiminate Transmetalation That Also Results in a More Active Olefin Polymerization Precatalyst. Organometallics. 2004, 23: 5885-5888.

Viswanathan, R.; Plotkin, M. A.; Prabhakaran, E. N.; Johnston, J. N. Free Radical-Mediated Aryl Amination and its Use in a Convergent [3+2] Strategy for Enantioselective Indoline a-Amino Acid Synthesis. Journal of the American Chemical Society. 2003, 125: 163-168.

Viswanathan, R.; Mutnick, D.; Johnston, J. N. The First Azacyclopentenyl Carbinyl Radical Isomerizations (ACCRI): Independent Use of Steric and Electronic (Polarization) Effects as Gating Elements. Journal of the Amercian Chemical Society. 2003, 125: 7266-7271.

Nugent, B. M.; Williams, A. L., Prabhakaran, E. N.; Johnston, J. N. Free Radical-Mediated Vinyl Amination: A Mild, General Pyrrolidinyl Enamine Synthesis. Tetrahedron. 2003, 59: 8877-8888.

Specialties

• VICB
• Organometallic Chemistry
• Organic Chemistry

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