Rick Bunt

Joseph Burr Professor of Chemistry & Biochemistry

 Fall 2017 - MBH 550: Wed: 11:15AM-1:15PM, Fri. 11:15AM-12:15PM, and by appointment
 McCardell Bicentennial Hall 550

Our research is motivated by a desire to understand how catalytic process occur at the detailed molecular level. In particular, we study palladium-catalyzed allylic-addition reactions and explore the functioning of chiral ligands. We are most interested in how three-dimensional “chiral information” is transmitted from the ligand, across the metal, to the reacting centers. We employ a combination of organic synthesis, physical organic methods, and one and two dimensional NMR spectroscopy, to study these reactions.

A series of chiral phosphinooxazoline (PHOX) ligands containing electron donating and withdrawing groups on the aryl backbone have been synthesized. The effects of these electronic perturbations are determined by measuring the enantiomeric excess of the alkylation and amination reaction products by chiral HPLC and by measuring the changes in the 13C NMR chemical shifts of the isolated p-allylpalladium intermediate complexes on the department's 400 MHz NMR spectrometer. The observed effects are then mathematically correlated to the electronic perturbations via Hammett and other types of linear free-energy relationship (LFER) analyses of the data.



Course List: 

Courses offered in the past four years.
indicates offered in the current term
indicates offered in the upcoming term[s]

CHEM 0103 - General Chemistry I      

General Chemistry I
Major topics will include atomic theory and atomic structure; chemical bonding; stoichiometry; introduction to chemical thermodynamics. States of matter; solutions and nuclear chemistry. Laboratory work deals with testing of theories by various quantitative methods. Students with strong secondary school preparation are encouraged to consult the department chair for permission to elect CHEM 0104 or CHEM 0107 in place of this course. CHEM 0103 is also an appropriate course for a student with little or no prior preparation in chemistry who would like to learn about basic chemical principles while fulfilling the SCI or DED distribution requirement. 3 hrs. lect., 3 hrs. lab, 1 hr. disc. DED SCI

Spring 2014

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CHEM 0203 - Organic I: Struct & Reactivity      

Organic Chemistry I: Structure and Reactivity
This course will provide students with an introduction to the structure and reactivity of organic molecules sufficient to continue directly to study of biochemistry (CHEM 0322). Topics covered will include models of chemical bonding, acid-base relationships, three-dimensional molecular structure (conformations and stereochemistry), reaction mechanisms and energy diagrams, substitution and elimination reactions, carbonyl reactions (additions, reductions, interconversions, and alpha-reactivity), and the fundamentals of biological molecules (carbohydrates, DNA, and RNA). Laboratory experiments will include purification techniques (recrystallization, distillation, extraction, and chromatography) as well as microscale organic reactions that complement the lecture portion of the course. (CHEM 0104 or CHEM 0107) 3 hrs. lect., 3 hrs. lab, 1 hr. prelab. SCI

Fall 2014, Spring 2015, Fall 2015

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CHEM 0204 - Organic II: Synthesis & Spect      

Organic Chemistry II: Synthesis and Spectroscopy
In this course we will explore the ways that organic molecules are made and their structures identified. The study of organic reactions will continue from CHEM 0203 with radical reactions, alkene and alkyne additions, aromatic reactions, oxidations and reductions, and additional carbonyl reactions. Emphasis in this course will be placed on using reactions in sequences to synthesize larger and more complex molecules. The theory and practice of mass spectrometry and UV-Vis, IR, and NMR spectroscopy will be studied as a means to elucidate the exact structures of organic molecules. Laboratory experiments will focus on synthetic techniques that complement the lecture portion of the course and the identification of complex unknowns via GC-MS, IR, and NMR. (CHEM 0203) 3 hrs. lect., 3 hrs. lab, 1 hr. prelab.

Spring 2016

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CHEM 0241 - Organic Chemistry I      

Organic Chemistry I
This course has been replaced by CHEM 0203, and will no longer be offered. SCI

Fall 2013

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CHEM 0301 - Medicinal Chemistry      

Medicinal Chemistry
Medicinal chemistry combines organic chemistry with biochemistry, analytical chemistry, physical chemistry, molecular biology, pharmacology, medicine, and related fields both to understand disease and to develop new pharmaceutical treatments (i.e., "drugs"). As chemists we try to correlate molecular structure with biological activity. In this course we will survey the major categories of diseases, drug targets, and drugs using a case-study approach. In addition to one mid-term exam, short oral presentations, and brief written assignments, the course will culminate with small-group based final projects (oral and written) about the design, development, and proposed future directions of pharmaceutical treatments targeting a specific disease. (CHEM 0203 or CHEM 0242) 3 hrs. lect.

Spring 2014, Spring 2016, Fall 2017

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CHEM 0312 - Inorganic & Physical Chemistry      

Inorganic and Physical Chemistry Laboratory
In this course students will carry out experiments in the field of inorganic and physical chemistry and write journal-style reports based on their results. In the first half of the semester students will conduct a multi-step synthesis and characterization of a Mo-Mo complex with a quadruple bond. Students will learn inert atmosphere synthetic techniques and how to use a glove box. The synthesized Mo-Mo complex will be characterized by UV-Vis, IR, 1H and 31P NMR spectroscopies, and cyclic voltammetry. In the second half of the semester students will conduct two physical chemistry experiments. First students will carry out a kinetic study of the isomerization of the Mo-Mo (alpha to beta or beta to alpha) complex by UV-Vis spectroscopy. Finally, students will obtain the high-resolution IR spectra of acetylene and deuterated acetylene and analyze the rotation-vibration spectra using statistical and quantum mechanics to obtain structural data and interpret the peak intensities. In addition to the laboratory activities, there will be lectures on metal quadruple bonds, principles of UV-Vis , IR, 1H and 31P NMR spectroscopies, cyclic voltammetry, and statistical mechanics. (CHEM 0311, CHEM 0351, and CHEM 0355. CHEM 0355 can be taken concurrently.) 3 hrs. lect. 3 hrs. lab

Spring 2015

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CHEM 0400 - Seminar In Chemical Research      

Seminar in Chemical Research
This seminar provides students with experiences to support the preparation of a senior thesis. As the course involves participation in a mentored laboratory project and the intent to complete a senior thesis, students must make arrangements to work with a faculty advisor prior to gaining approval for course registration. The classroom portion of this seminar focuses on reading the scientific literature, giving effective oral presentations, and writing the thesis introduction. Particular emphasis will be given to computer and technology issues related to oral and written presentations. Participation will normally be followed by registration for CHEM 0500 or CHEM 0700 (winter term and spring). (Senior standing; Approval only) 2 hrs. sem., 12 hrs. lab.

Fall 2014

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CHEM 0500 - Independent Study      

Independent Study Project
Individual study for qualified students. (Approval required)

Fall 2013, Winter 2014, Spring 2014, Fall 2014, Winter 2015, Spring 2015, Fall 2015, Winter 2016, Spring 2016, Fall 2016, Winter 2017, Spring 2017, Fall 2017, Spring 2018

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CHEM 0700 - Senior Research      

Senior Research
In this course students complete individual projects involving laboratory research on a topic chosen by the student and a faculty advisor. Prior to registering for CHEM 0700, a student must have discussed and agreed upon a project topic with a faculty member in the Chemistry and Biochemistry Department. Attendance at all Chemistry and Biochemistry Department seminars is expected. (Approval required; open only to seniors)

Fall 2013, Winter 2014, Spring 2014, Fall 2014, Winter 2015, Spring 2015, Fall 2015, Winter 2016, Spring 2016, Fall 2016, Winter 2017, Spring 2017, Fall 2017, Spring 2018

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CHEM 0701 - Senior Thesis      

Senior Thesis
Students who have initiated research projects in CHEM 0400 and who plan to complete a senior thesis should register for CHEM 0701. Students are required to write a thesis, give a public presentation, and defend their thesis before a committee of at least three faculty members. The final grade will be determined by the department. Attendance at all Chemistry and Biochemistry Department seminars is expected. (CHEM 0400; approval required)

Fall 2013, Winter 2014, Spring 2014, Fall 2014, Winter 2015, Spring 2015, Fall 2015, Winter 2016, Spring 2016, Fall 2016, Winter 2017, Spring 2017, Fall 2017, Spring 2018

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FYSE 1259 - Science and Science Fiction      

Science and Science Fiction
More than just robots and rocket ships, science fiction frees us from the bounds of Earth’s present condition and allows us to explore alternate possibilities and futures, both positive and negative, for humankind. Often by confronting things decidedly non-human we discover more about what it means to be human. We will read both science fact (i.e., non-fiction) and science fiction literature to try to understand more about our humanity, our present world, and what might become of each in the future. Topics will include space travel, energy and the environment, the nature of the universe, and the meaning of life. We will write both fact-based essays and science fiction short stories. 3 hrs. sem. CW

Fall 2017

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MBBC 0700 - Senior Research      

Senior Thesis
Seniors conducting independent study in Molecular Biology and Biochemistry should register for MBBC 0700 unless they are completing a thesis project in which case they should register for MBBC 0701. (Approval required).

Fall 2015, Fall 2016, Fall 2017

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MBBC 0701 - Senior Thesis      

Senior Thesis
Students conducting independent thesis research in Molecular Biology and Biochemistry must register for MBBC 0701 while completing research projects initiated in BIOL 0500, MBBC 0700, or CHEM 0400. Students will organize and lead regular discussions of their research and research methods, and attend weekly meetings with their designated laboratory group to foster understanding of their special area, and practice the stylistic and technical aspects of scientific writing needed to write their thesis. (CHEM 0400 or BIOL 0500 or MBBC 0700) (Approval required).

Winter 2015, Winter 2016, Spring 2016, Winter 2017, Spring 2017, Spring 2018

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Recent Awards

2007 Perkins Award for Excellence in Teaching

Recent Publications

Bryan S. Holtzman,# Eric T. Roberts,# Nicholas S. Caminiti,# Jacob A. Fox,# Madison B. Goodstein,# Staci A. Hill,# Zitong B. Jia,# Isabelle N. –M. Leibler,# Michael L. Martini,# Gina M. Mendolia,# Molly S. Costanza-Robinson, and Richard C. Bunt, Ligand and base additive effects on the reversibility of nucleophilic addition in palladium-catalyzed allylic aminations monitored by nucleophile crossover. Tetrahedron Lett. 2017, 58, 432.

*Nicholas S. Caminiti,*Madison B. Goodstein, *Isabelle N.-M . Leibler,*Bryan S. Holtzman, *Zitong B. Jia,  *Michael L. Martini, *Nathaniel C. Nelson,and Richard C. Bunt, Reversible nucleophilic addition can lower the observed enantioselectivity in palladium-catalyzed allylic amination reactions with a variety of chiral ligands. Tetrahedron Lett. 2015, 56, 5445.

Richard C. Bunt, Charlotte Majerczyk, Mitchell Brittnacher, Michael Jacobs, Christopher Armour, Matthew Radey, Hillary Hayden, Ryland Bydalek, and E. Peter Greenberg, “A cross-species comparison of the Burkholderia pseudomallei, Burkholderia thailandensis, and Burkholderia mallei quorum sensing regulons,” Journal of Bacteriology 2014, 196, 22, 3862.

Richard C. Bunt, Charlotte Majerczyk, Mitchell Brittnacher, Michael Jacobs, Christopher D. Armour, Mathew Radey, Emily Schneider, Somsak Phattarasokul, and E. Peter Greenberg, “Global Analysis of the Burkholderia thailandensis Quorum Sensing-Controlled Regulon,” Journal of Bacteriology, 2014, 196, 7, 1421.

Charlotte Majerczyk, Mitchell Brittnacher, Michael Jacobs, Christopher D. Armour, Mathew Radey, Emily Schneider, Somsak Phattarasokul, Richard Bunt and E. Peter Greenberg “Global Analysis of the Burkholderia thailandensis Quorum Sensing-Controlled Regulon” J. Bacteriol. 2014, 196, 7, 1412.

Charlotte Majerczyk, Loren Kinman, Tony Han, Richard Bunt, and E. Peter Greenberg “Virulence of Burkholderia mallei Quorum-Sensing Mutants” Infect. Immun. 2013, 81, 5, 1471.

*Armstrong, P.B., *Dembicer, E.A., *Desbois, A.J., *Fitzgerald, J.T., *Gehrmann, J.K., *Nelson, N.C., *Noble, A.L., Bunt, R.C. “Investigation of the Electronic Origin of Asymmetric Induction in Palladium-Catalyzed Allylic Substitutions with Phosphinooxazoline (PHOX) Ligands by Hammett and
Swain–Lupton Analysis of the 13C NMR Chemical Shifts of the (π-Allyl)palladium Intermediates.” Organometallics 2012, 31, 6933-6946. DOI: 10.1021/om3007163

Paul B. Armstrong,# Lisa M. Bennett, Ryan N. Constantine,# Jessica L. Fields,# Jerry P. Jasinski, Richard J. Staples, Richard C. Bunt "Hammett 13C NMR and X-ray studies of allylpalladium phosphinooxazoline chiral ligand complexes", Tetrahedron Lett. 2005, 46, 1441-1445.

Sunhee Choi, Richard B. Cooley,# Amanda S. Hakemian, # Yuna C. Larrabee, Richard C. Bunt, Stéphane D. Maupas, James G. Muller, and Cynthia J. Burrows, "Mechanism of Two-Electron Oxidation of Deoxyguanosine 5'-Monophosphate by a Platinum(IV) Complex" J. Am. Chem. Soc. 2004, 126, 591.

Ryan N. Constantine,# Naomi Kim,# and Richard C. Bunt, "Hammett Studies of Enantiocontrol by PHOX Ligands in Pd-Catalyzed Allylic Substitution Reactions" Org. Lett. 2003, 5, 2279.


2007 American Chemical Society-Petroleum Research Fund, "Hammett Studies of P,N-Chiral Ligands." 9/1/07- 8/31/10 ($55,000)

2007 National Science Foundation (NSF-RUI, CHE-0714541) "Hammett Studies of P,N-Chiral Ligands.", 8/15/07- 8/14/10 ($146,000)

2005 Vermont Genetics Network (NIH-BRIN), Equipment Grant for "A Solvent Purification System" Co-PI with Jeff Byers ($24,700)

2003 National Institutes of Health (NIH-AREA), "Mechanism of Base-Flipping by DNA Modifying Enzymes" ($137,971)

2003 Pfizer Summer Undergraduate Research Fellowship for Sarah S. Goodwin ($5,000)

2002 Vermont Genetics Network (NIH-BRIN), Partial Sabbatical Leave Support for "Altering the Rate of Base Flipping in DNA" ($20,000) 

2001 American Chemical Society-Petroleum Research Fund, Type G, "Probing the Electronic Origins of Chiral Ligand Asymmetry in Palladium-Catalyzed Allylic-Alkylation Reactions" ($25,000)

2001 Cottrell College Science Award from Research Corporation, "Probing the electronic origins of chiral ligand asymmetry in palladium-catalyzed allylic-aklylation reactions" ($41,381)

2000 Pfizer Summer Undergraduate Research Fellowship for Agnes Makingwe ($5,000)

2000 VT EPSCoR Award, "Electronic Control of Chiral Ligand Asymmetry" ($5,500)


Department of Chemistry & Biochemistry

McCardell Bicentennial Hall
276 Bicentennial Way
Middlebury College
Middlebury, VT 05753