Synthetic Organic Chemistry

Robert Maleczka

Professor

540 CEM

517-353-0834


Chairperson

485B CEM

517-353-1086


Research webpage


Primary Research Area

Organic (Or)

Other Area(s) of Interest

Organometallic (Om)

Research

(Research Description PDF)

Our group is interested in a) the total synthesis of biologically important natural products, b) the invention of new reactions and strategies in organic synthesis, and c) green chemistry.

Green Chemistry: Central to our research is the development of efficient and environmentally benign reactions and strategies.  The Pharmaceutical Roundtable of the American Chemical Society’s Green Chemistry Institute deemed cross-couplings that avoid haloaromatics as their top aspirational reaction.  In collaboration with Professor Mitch Smith, we are inventing such reactions.  Specifically, we are using catalytic C–H activation/borylation, often combined with subsequent chemical events, to generate pharmaceutically relevant building blocks for organic synthesis and the late stage functionalization of drugs and drug candidates.

Another of our green chemistry ventures aims to minimizing the need for tin in various processes. For example, we have developed an allylation/hydrostannation sequence where the tin waste from the allylation is recycled in situ so as to allow its use in the hydrostannation. This chemistry employs polymethylhydrosiloxane (PMHS), which is an oligomeric non-toxic waste product of the silicon industry, as the stoichiometric reductant.

Invention of New Reactions: The principles of green chemistry also motivate us to create new synthetic methods. Here we have been focusing on the employment of organosilanes as both reagents and substrates in chemical transformations ranging from Wittig rearrangements to new approaches to double-decker silsesquioxanes (DDSQ’s) for polymer applications.  As part of a collaboration with Dow Chemical, we have also used PMHS in conjunction with our borylation chemistry to regioselectively generate building blocks of interest to the agrochemical industry.  Here the combination of Pd(OAc)2 and PMHS generates siloxane encapsulated Pd(0) nanoclusters.

Total Synthesis:  The unifying thesis behind all of our methodological and mechanistic studies is that the chemistry to emerge from such studies should be applicable to real synthetic problems.  We view target synthesis as the best proof of this concept.  For example, as part of our green chemistry program, we look to make TMC-95A and autolytimycin by the strategic application of our own synthetic methods.

Selected Publications

Separation of Asymmetrically Capped Double-Decker Silsesquioxanes Mixtures, Vogelsang, D. F.; Dannatt, J. E.; Maleczka, R. E., Jr.; Lee, A. Polyhedron 2018, 155, 189–193.

Cobalt-Catalyzed C-H Borylation of Alkyl Arenes and Heteroarenes Including the First Selective Borylations of Secondary Benzylic C–H Bonds, Jayasundara, C. R. K.; Sabasovs, D.; Staples, R. J.; Oppenheimer, J.; Smith, M. R., III Maleczka, R. E., Jr., Organometallics 2018, 37, 1567-1574.

Achieving High Ortho Selectivity in Aniline C-H Borylations by Modifying Boron Substituents, Smith, M. R., III; Bisht, R.; Haldar, C.; Pandey, G.; Dannatt, J. E.; Ghaffari, B.; Maleczka, R. E.; Jr.; Chattopadhyay, B., ACS Catal. 2018, 8, 6216-6223.

Catalytic Hydrodehalogenation Reactions, Ghosh, B.; Maleczka, R. E., Jr., in Science of Synthesis: Catalytic Reduction in Organic Synthesis Vol. 1 (DOI: 10.1055/b-005- 145236); de Vries, J. G., Ed.; Georg Thieme Verlag KG: Stuttgart 2018; pp. 355–373.

Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental / in Silico Strategy for Optimizing Weak Interactions, Chattopadhyay, B.; Dannatt, J. E.; Andujar-De Sanctis, I. L.; Gore, K. A.; Maleczka, R. E.; Jr.; Singleton, D. A.; Smith, M. R., III, J. Am. Chem. Soc. 2017, 139, 7864–7871.

Bismuth Acetate as a Catalyst for the Sequential Protodeboronation of Di- and Triborylated Indoles, Shen, F.; Tyagarajan, S.; Perera, D.; Krska, S. W.; Maligres, P. E.; Smith, M. R., III; Maleczka, R. E.; Jr., Org. Lett. 2016, 18, 1554–1557.

Improved Synthesis of Electron Deficient Bipyridines, Li, H.; Oppenheimer, J.; Smith, M. R., III; Maleczka, R. E.; Jr., Tetrahedron Lett. 2016, 57, 2231–2232.

Harnessing C–H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization, Kallepalli, V. A.; Gore, K. A.; Shi, F.; Sanchez, L.; Chotana, G. A.; Miller, S. L.; Maleczka, R. E., Jr.; Smith, M. R., III, J. Org. Chem. 2015, 80, 8341–8353

CV

B.S., 1984, Univ. of Illinois at Urbana-Champaign

Abbott Labs, 1984-1987

Ph.D., 1992, The Ohio State Univ.

Postdoctoral Fellow, 1992-1995, American Cancer Society Univ. of Pennsylvania

Awards/Honors

2014 ACS Fellow
2013 Meritorious Faculty Award by the College of Natural Science Alumni Association
2013 Merck Technology Symposium's Technology Collaboration Award
2008 Presidential Green Chemistry Challenge Award
2003 - 2004 Smith First Edition Board of Advisors McGraw Hill
2001 Teacher-Scholar Award Michigan State University (College of Natural Science)
2001 - 2004 Yamanouchi USA Foundation Faculty Award Yamanouchi USA Foundation
2000 Junior Faculty Award Sigma Xi Honor Society (Michigan State University)
2000 Novartis Lecturer Yale University
2000 - 2003 NSF Career Award National Science Foundation
1998 Advisory Board Member National Organization for the Professional Advancement of Black Chemists and Chemical Engineers
1998 MSU Senior Class Council Outstanding Faculty Award Nominee Michigan State University (Senior Class Council)
1998 - 2001 NIH First Award National Institutes of Health
1998 MSU Chapter Mentor of the Year National Organization for the Professional Advancement of Black Chemists and Chemical Engineers
1993 - 1995 Postdoctoral Fellow American Cancer Society
1992 Ph.D. The Ohio State University
1987 - 1992 Graduate Research Associate The Ohio State University
1984 - 1987 Research Assistantship Abbott Laboratories
1984 Bachelor of Science University of Illinois, Urbana-Champaign
1983 - 1984 Undergraduate Research University of Illinois, Urbana-Champaign
1980 - 1982 Air Force ROTC Scholarship Air Force ROTC
Dean's List University of Illinois, Urbana-Champaign