Michael Harmata

Professor Michael Harmata
Rabjohn Distinguished Professor of Chemistry
Phone: 
573-882-1097
Office: 
332 Chemistry
Research Emphasis: 

Synthetic and Medicinal Organic Chemistry, (4+3)-Cycloadditions, Synthesis and Chemistry of Benzothiazines, Cyclopentadienone Chemistry, Retro-Nazarov Reaction, Kagan's Ether Chemistry, Trögers Base Chemistry, Silver Ion Catalysis, Allenic Sulfone Chemistry, Fluorination and Total Synthesis

Education: 

AB, University of Illinois-Chicago, 1980
PhD, University of Illinois-Urbana, 1985

Professional Experience: 

Norman Rabjohn Distinguished Professor of Chemistry, 2000-present
Professor, University of Missouri, 1998-2000
Associate Professor, University of Missouri, 1992-1998
Assistant Professor, University of Missouri, 1986-1992
NIH Postdoctoral Fellow, Stanford University, 1985-1986

Honors and Awards

2018: Invited Guest Professor, University of Giessen
2018: Research Fellowship, Alexander von Humboldt Foundation (Reinvitation)
2015-2016: Leadership Development Program, University of Missouri System
2015: Fuldner Faculty Fellow, University of Missouri-Columbia
2014: Invited Guest Professor, University of Giessen
2014: Fuldner Faculty Fellow, University of Missouri
Oct 21, 2011: Sigma-Aldrich Lectureship, University of Nevada-Reno
2011: Invited Guest Professor, University of Strasbourg
2011: Japan Society for the Promotion of Science Fellow
2010: Prose Award-Honorable Mention-for Silver in Organic Chemistry
2010: Adjunct Professor, International Institute of Nano and Molecular Medicine
2010-present: Liebig Professorship, University of Giessen
2008: Research Fellowship, Alexander von Humboldt Foundation (Reinvitation)
2006: Big 12 Faculty Fellow, University of Texas-Austin
2000: Norman Rabjohn Distinguished Professorship, University of Missouri
1998: Research Fellowship, Alexander von Humboldt Foundation
1997: Arts and Science Student Government "Blue Chalk" Advising Award
1985: NIH Postdoctoral Fellowship, Stanford University
 

Selected Professional Activities

Chair-Elect, University of Missouri Local Section of the American Chemical Society, 2019
Chair, University of Missouri Local Section of the American Chemical Society, 2018
Chair-Elect, University of Missouri Local Section of the American Chemical Society, 2017
Member, ACS Awards Committee, 2016-2018
Chair, University of Missouri Local Section of the American Chemical Society, 2016
Editorial Board, Chemistry SELECT, 2015-present
Chair-Elect, University of Missouri Local Section of the American Chemical Society, 2015
Chair, University of Missouri Local Section of the American Chemical Society, 2014
Chair-Elect, University of Missouri Local Section of the American Chemical Society, 2013
Editorial Board, Letters in Organic Chemistry, 2007-2010
Chair, Gordon Research Conference on Organic Reactions and Processes, 2000
Vice-Chair, Gordon Research Conference on Organic Reactions and Processes, 1999
Editor: Advances in Cycloaddition, 1997-2001
Editor: Strategies and Tactics in Organic Synthesis, 2002-present
Editorial Board, Mini Reviews in Organic Chemistry, 2003-present
Chair, University of Missouri Local Section of the American Chemical Society, 1993
President, President, Sigma Xi, University of Missouri Local Chapter, 1992-1993
Chair-Elect, University of Missouri Local Section of the American Chemical Society, 1992
Vice-President, Vice-President, Sigma Xi, University of Missouri Local Chapter, 1991-1992
National Chemistry Week, 1989.  Appeared on Missouri Forum, a local television talk show, to debate an environmentalist regarding the impact of chemistry on society.  The local ACS section was subsequently given an award from the national organization for the best media coverage of NCW activities as a result of this program.
 
Research: 

My research program encompasses many areas of organic chemistry with a principal focus on pericyclic reactions of reactive intermediates.  We have also made significant contributions to molecular recognition and supramolecular chemistry in the course of our work on derivatives of Kagan’s ether and Tröger’s base.

In the area of (4+3)-cycloaddition chemistry, we are now especially interested in new mild methods to generate allylic cations. Our newest work is centered on the development of asymmetric processes and the application of methodology we have invented to the synthesis of biologically active natural products, compounds which served as drug leads or important tools for discovering the molecular mechanism by which small molecular produce their effects in living systems.

Our work with Kagan's ether and Tröger's base centers on the development of new chiral templates for applications in catalysis, molecular recognition and supramolecular chemistry. One current goal is developing a series of molecules for a process we call asymmetric charge transfer catalysis.  Another concerns the design and synthesis of new ligands for the actinide elements

We are actively engaged in allenic sulfone and allylic sulfone chemistry.  We have developed methods for the synthesis of value-added, boronated allylic sulfones and have invented a number of new processes that increase the synthetic value of allenic sulfones.

Finally, the construction of new chiral ligands for applications in asymmetric catalysis is one goal of our work involving the cyclic sulfoximines known as benzothiazines. We have also developed methodology that is applicable to the asymmetric total synthesis of a wide variety of natural products, including those of the pseudopterosin class. These compounds have biological activities that include powerful analgesic effects and potent antitubercular activity.

Select Publications: 

“Synthesis of Methyl 2-Bromo-2 oxoccyclopent-1-enecarboxylate.”  Rama Rao Tata and Michael Harmata.  Org. Synth. 2018, 95, 425-438.

“Synthesis of 3-Arylsulfonyl-3-Pyrrolines from Allenyl Sulfonamides by Silver Ion Catalysis.”  Rama Rao Tata, Chencheng Fu, Steven P. Kelley, and Michael Harmata.  Organic Letters 2018, 5723-5726.

“Synthesis of (Z)-2-[(tert-Butyldimethylsilyl)oxy]-3-(phenylthio)acrylaldehyde.”  Michael Topinka and Michael Harmata.  Synthesis 2018, 4476-4482.

“Derivatives of Alkyl 2-Hydroxy-3-oxocyclopent-1-enecarboxylates and Intermolecular [4+2] Cycloadditions of Cyclopentadienones Prepared Therefrom.”  Aswin Garimalla and Michael Harmata.  Synthesis 2018, 4483-4489.

“Sulfinate Allenyl Carbenoids: Synthesis of 2,​5-​Dihydrofurans by Domino Rearrangement and Cyclization.”  Rama Rao Tata and Michael Harmata.  European Journal of Organic Chemistry 2018, 372-375.

“(4+3)-Cycloaddition Reactions of N-Alkyl Oxidopyridinium Ions.”  Chencheng Fu, Nestor Lora, Patrick L. Kirchhoefer, Dong Reyoul Lee, Erich Altenhofer, Charles L. Barnes, Natasha L. Hungerford, Elizabeth H. Krenske, and Michael Harmata.  Angewandte Chemie, International Edition 2017, 56, 14682-14687.

“Comments on a CIP rule conundrum:  Why I think I’m right.”  Michael Harmata.  Tetrahedron Letters 2017, 58, 3687-3689.

“An Asymmetric, Catalytic (4+3) Cycloaddition Reaction of Cyclopentenyl Oxyallylic Cations.”  Michael Topinka, Kerstin Zawatzky, Charles L. Barnes, Christopher J. Welch, and Michael Harmata.  Organic Letters 2017, 19, 4106-4109.

“Electrophilic Trapping of α-Lithio Dienyl Sulfones.”  Carissa S. Hampton and Michael Harmata.  Tetrahedron Letters 2017, 58, 2530-2532.

“In vivo Transport of Three Radioactive [18F]-Fluorinated Deoxysucrose Analogs by the Maize Sucrose Transporter ZmSUT1.”  Thu M. Tran, Carissa S. Hampton, Tom W. Brossard, Michael Harmata, J. David Robertson, Silvia S. Jurisson, and David M. Braun.  Plant Physiology and Biochemistry 2017, 115, 1-11.

“Preparation of Propargylic Sulfinates and Their [2,3]-Sigmatropic Rearrangement to Allenic Sulfones.”  Rama Rao Tata, Carissa S. Hampton, and Michael Harmata.  Advanced Synthesis and Catalysis 2017, 359, 1232–1241.

“Synthesis, Characterization, and In Vitro Evaluation of New 99mTc/Re(V)-Cyclized Octreotide Analogues: An Experimental and Computational Approach.”  Yawen Li, Lixin Ma, Vikram Gaddam, Fabio Gallazzi, Heather M. Hennkens, Michael Harmata, Michael R. Lewis, Carol A. Deakyne, and Silvia S. Jurisson.  Inorganic Chemistry 2016, 55, 1124-1133.

“Mechanistic Aspects of the Palladium-Catalyzed Isomerization of Allenic Sulfones to 1-Arylsulfonyl 1,3-Dienes.” Carissa S. Hampton and Michael Harmata.  The Journal of Organic Chemistry 2016, 82, 4807-4822.

“Synthesis of Tröger’s Base Derived Ligands: PHZ-Derivatized Ligand with Pendant Donor Arms.”  Carissa S. Hampton and Michael Harmata.  Tetrahedron 2016, 6064-6077.

“Metal-Catalyzed (4+3) Cycloadditions Involving Allylic Cations.”  Darin E. Jones and Michael Harmata.  Science of Synthesis, Metal-Catalyzed Cyclization Reactions 2 2016, 319-382.

“Silver-Catalyzed Cyclization of Sulfonyl Allenes to Dihydrofurans.”  Rama Rao Tata and Michael Harmata.  Organic Letters 2016, 5684–5687.

“Radiosynthesis of 6'-deoxy-6'[¹⁸F]fluorosucrose via Automated Synthesis and its Utility to Study in vivo Sucrose Transport in maize Zea mays Leaves.”  David Rotsch, Tom Brossard, Saadia Bihmidine, Weijiang Ying, Vikram Gaddam, Michael Harmata, J. David Robertson, Michael Swyers, Sylvia Jurisson, and David M. Braun..  PLOS ONE 2015 10(5): e0128989.  doi:10.1371/journal.pone.0128989.

“[2,3]-Sigmatropic Rearrangement of Propargylic Sulfinates by a Pale Cu1-USY Zeolite and Copper Salts.”  Carissa S. Hampton and Michael Harmata.  Tetrahedron Letters 2015, 56, 3243-3245.

“The Resolution and Determination of the Absolute Configuration of a Twisted Bis-Lactam Analogue of Tröger´s Base: a Comparative Spectroscopic and Computational Study.”  Ögmundur Vidar Rúnarsson, Christian Benkhäuser, Niels Johan Christensen, Josep Artacho Ruiz, Erhad Ascic, Michael Harmata, Victor Snieckus, Kari Rissanen, Peter Fristrup Arne Lützen, and Kenneth Wärnmark.  The Journal of Organic Chemistry, 2015, 80, 8142–8149.

“A Protocol for the exo-mono and exo,exo-bis Functionalization of the Diazocine Ring of Tröger’s Base.”  Sami Dawaigher,  Kristoffer Månsson, Erhad Ascic, Josep Artacho, Roger Mårtensson, Nagarajan Loganathan, Ola F. Wendt, Michael Harmata, Victor Snieckus, and Kenneth Wärnmark.  The Journal of Organic Chemistry, 2015, 81, 12006-12014.

“Mechanistic Aspects of the Phosphine-Catalyzed Isomerization of Allenic Sulfones to 2-Arylsulfonyl-1,3-Dienes.”  Carissa S. Hampton and Michael Harmata. The Journal of Organic Chemistry, 2015, 81, 12151-12158.

“Radical Isomerization of Borylated Allylic Sulfones.”  Erich Altenhofer and Michael Harmata.  Tetrahedron Letters 2015, 56, 3176-3178.

“[2,3]-Sigmatropic Rearrangement of Propargylic Sulfinates by a Pale Ag1-USY Zeolite and Silver Salts.”  Carissa S. Hampton and Michael Harmata.  Advanced Synthesis and Catalysis 2015, 357, 549-552.

“Suzuki-Miyaura Coupling Reactions of Conjunctive Reagents:  2-Borylated Allylic Sulfones.”  Erich F. Altenhofer and Michael Harmata.  The Journal of Organic Chemistry, 2015, 80, 8168–8174.

“Computational Analysis of the Stereochemical Outcome in Harmata’s Catalytic Asymmetric (4+3)-Cycloaddition Reaction.”  Elizabeth Krenske, Kendall Houk and Michael Harmata.  The Journal of Organic Chemistry 2015, 80, 744–750.

“A Synthesis of Dihydrofuran-3(2H)-ones.”  Rama Rao Tata and Michael Harmata.  The Journal of Organic Chemistry, 2015, 80, 6839–6845.

“The Quasi-Favorskii Rearrangement.”  Michael Harmata.  In Molecular Rearrangements in Organic Synthesis; Rojas, C. M., Ed.; John Wiley & Sons:  Hoboken, 2015; Chapter 7.

“[2,3]-Sigmatropic Rearrangement of Propargylic Sulfinates by a Pale Cu1-USY Zeolite and Copper Salts.  Carissa S. Hampton and Michael Harmata.  Tetrahedron Letters 2015, 56, 3243-3245.

“A Synthesis of 6-Deoxy-6-Fluorosucrose Suitable for PET Applications.”  Xuefeng Gao, Vikram Gaddam and Michael Harmata.  Carbohydrate Research 2014, 400, 14-18.

“Catalytic Generation of Vinylthionium Ions.  (4+3)-Cycloadditions and Friedel-Crafts Alkylations.”  Michael Topinka, Rama Rao Tata and Michael Harmata.  Organic Letters 2014, 16, 4476–4479.

“A New Synthesis of α’-Hydroxydienones.”  Rama Rao Tata, Carissa S. Hampton, Erich F. Altenhofer, Michael Topinka, Weijiang Ying, Xuefeng Gao and Michael Harmata.  Chemistry A European Journal 2014, 20, 13547–13550.

“Regiodivergent Synthesis of 1- and 2-Arylsulfonyl-1,3-Dienes.”  Carissa S. Hampton and Michael Harmata.  Organic Letters 2014, 16, 1256–1259.

“Synthesis of Functionalized Cyclic Boronates.”  Erich Altenhofer and Michael Harmata.  Organic Letters 2014, 16, 1-4.

“Carbon to Carbon Anion Relay Chemistry:  Facile Generation of Substituted Allyllithium Species.” Pinguan Zheng, Zhengxin Cai, Aswinkumar Garimallaprabhakaran, Parham Rooshenas, Peter R. Schreiner, and Michael Harmata.  European Journal of Organic Chemistry 2011, 5255-5260.

“Control Elements in Dynamically Determined Selectivity on a Bifurcating Surface.” Jacqueline B. Thomas, Jack R. Wass, Michael Harmata and Daniel A. Singleton.  Journal of the American Chemical Society 2008, 130, 14544-14555.

“An Interrupted [4+3]-Cycloaddition Reaction:  A Hydride Shift (Ene Reaction)   Intervenes.” Michael Harmata, Chaofeng Huang, Parham Rooshenas and Peter R. Schreiner.  Angew. Chem., Int. Ed. 2008, 8696-8699.

“Intermolecular [4+2]-Cycloaddtions of a Reactive Cyclopentadienone.”  Michael Harmata and Maria G. Gomes.  European Journal of Organic Chemistry 2006, 2273-2277.

“Deantiaromatization as a Driving Force in an Electrocyclic Reaction.” Michael Harmata, Pinguan Zheng, Peter R. Schreiner and Armando Navarro-Vázquez, Angewandte Chemie, International Edition 2006, 45, 1966-1971.

“Benzothiazines in Synthesis.  A Synthesis of Pseudopteroxazole.”  Michael Harmata and Xuechuan Hong.  Organic Letters 2005, 8, 3581-3583.

“Chiral Molecular Tweezers.”  Michael Harmata, Accounts of Chemical Research 2004, 37, 862-873.

"Asymmetric Organocatalysis of 4+3 Cycloaddition Reactions."  Michael Harmata, Sunil    K. Ghosh, Xuechuan Hong, Sumrit Wacharasindhu and Patrick Kirchhoefer. Journal of the American Chemical Society, 2003, 125, 2058-2059.

"The Retro-Nazarov Reaction."  Michael Harmata and Dong Reyeoul Lee.  Journal of the American Chemical Society 2002, 124, 14328-14329.

“Molecular Clefts.  4.  An Approach to Structural Analogues of Echinomycin:  Synthesis of a New Class of Synthetic Molecular Tweezers.”  Michael Harmata, Charles L. Barnes, Srinivasa Rao Karra and Saleh Elahmad.  Journal of the American Chemical Society 1994, 116, 8392-8393.

“Alkoxyvinyl Thionium Ions in Intramolecular 4+3 Cycloaddition Reactions.”  Michael   Harmata, Vernon R. Fletcher and R.J. Claassen II.  Journal of the American Chemical Society 1991, 113, 9861-9862.

 

Research Division: