Chemistry Department
Professor
Ph.D., Boston College
Fields: Organic, Bioorganic
Email: bsculimb@holycross.edu
Office Phone: 508-793-3425
Office: Haberlin 332
Lab: Smith Laboratories 357
PO Box: C
Organic Chemistry is ...
"The study of the world’s best element, carbon, and how it interacts with its best friends, hydrogen, nitrogen and the halogens and other compounds that have carbon."
"The study of our extremely versatile friend carbon and its many adventures in displaying the unique and divine in the universe through order, geometry and in forming a myriad of new possibilities."
"Extremely colorful with a wide assortment of ingredients containing carbon, oxygen, and hydrogen (nitrogen too!) and many different recipes that will make desired goods."
from the final exam for Chem 221 (spring 2007)
The Scullab is an organic methodology group focused on the chemical synthesis of phosphates and other biomimetics. Phosphates are a ubiquitous functional group within biological systems that are incorporated in critical molecules such as DNA, RNA, proteins and small molecule messengers such as ATP and inositol phosphates. The development of new and more efficient methods for forming phosphorylated compounds can impact the treatment of diseases where phosphorylation is aberrant (such as cancer), initiate the use of phosphorylated small molecules in disease treatment and answer fundamental questions about the nature of this chemical structure.
Research in our group focuses on the development of new methods to phosphorylate alcohols utilizing both phosphorous (III) and phosphorous (V) reagents. Key questions for our lab are:
- What is the phosphate source?
- What catalysts are effective?
- What protecting groups can we use on phosphorus?
- If two or more hydroxyl groups are present, how do we selectively phosphorylate just one?
Chemistry 221 - Organic Chemistry I
A study of organic compounds from the points of view of the chemistry of the functional groups, modern structural theory and reaction mechanisms. The chemistry of aliphatic hydrocarbons, alkenes, dienes and alkyl haildes is introduced in a discovery mode. Substitution, addition and elimination mechanisms are studied in detail. Emphasis is placed on stereochemistry. One four-hour "discovery" laboratory session per week is included. Students learn various separation, purification and identification (chemical and spectroscopic) of organic compounds in the laboratory. There is an emphasis on one-step synthetic conversions which introduce the reactions studied in the lecture course.
Prerequisite: Chem 181
Chemistry 222 - Organic Chemistry II
A continuation of Chemistry 221. Aromatic compounds, alcohols, ethers, aldehydes, ketones, amines, carboxylic acids and their deriviatives are studies. Aromatic substitution, acyl transfer and carbonyl condensation reactions are developed. The mechanistic implications and synthetic application of these organic reactions are evaluated. One four-hour "discovery" laboratory session per week is included. Microscale synthetic techniques are included.
Prerequisite: Chem 221
Chemistry 301 - Biochemistry
A detailed study of the chemistry of biological molecules, with a focus on the structure of biological macromolecules and the chemical mechanism of biochemical transformations. Topics may include the structure and synthesis of proteins, nucleic acids, carbohydrates and lipids, enzymatic catalysis, biological thermodynamics, glycolysis and gluconeogenesis, the citric acid cycle, fatty acid oxidation, oxidative phosphorylation, and metabolic regulation. A strong background in thermodynamics and organic chemistry is highly recommended. This course may serve as a prerequisite for Biology 302. Students may not count both Biology 301 and Chemistry 301 for credit.
Prerequisites: Chemistry 222 and 231
Chemistry 305 - Mechanistic Organic Chemistry
There are critical and at times subtle factors that influence organic reactions. These factors will be illustrated through specific case studies. The case studies will demonstrate how experimental data is used to develop mechanistic knowledge about a reaction. The course will aim to develop skills for thinking critically and logically about the mechanism of organic reactions.
Prerequisite: Chem 222
Chemistry 141 – Chemistry of Food
This course addresses the chemical components of food and the chemical processes involved in cooking. Have you ever wondered why Julia Child whips egg whites in copper bowls? why certain foods expand during cooking? Or why different cookie recipes require different baking temperatures? We will look into the science that explains these food wisdoms by a combination of lecture, discussions, and food-chemistry experiments. We will also discuss the nutrients in food, how they are enhanced or altered by cooking, and the role this plays in human nutrition. This class is suited for non-science majors. Students may not enroll in this course if they have previously taken Chemistry 181.
(19) “Catalyst identification for chemoselective phosphorylation of phenols and aliphatic alcohols” E.M. Eason*, W.J. Reller*, Katerine R. Fazekas*, B.R. Sculimbrene Tetrahedron Lett. 2023, 129, 154680.
(18) “Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst” E.T. Ouellette, M.G. Lougee, A.R. Bucknam, P.J. Endres, J.Y. Kim, E.J. Lynch, E.J. Sisko, B.R. Sculimbrene, J. Org. Chem. 2021, 86, 7450-7459.
(17) “Outer-Sphere Control for Divergent Multicatalysis with Common Catalytic Moieties” C.R. Shugrue, B.R. Sculimbrene, E.R. Jarvo, S.J. Miller J. Org. Chem. 2019, 84, 1664-1672.
(16) "Synthesis of alpha-chiral-beta,gamma-unsaturated carboxylic acid derivatives using chiral auxiliaries" K.E. Poremba, V.A. Lee, B.R. Sculimbrene Tetrahedron, 2014, 70, 5463-5467.
(15) "Selective Phosphorylation of Diols with a Lewis Acid Catalyst" K.A. Coppola, J.W. Testa, E.E. Allen, and B.R. Sculimbrene Tetrahedron Lett. 2014, 55, 4203-4206.
(14) "Catalytic Lewis Acid Phosphorylation with Pyrophosphates" O.S. Fenton, E.E. Allen, K.P. Pedretty, S.D. Till, J.E. Todaro and B.R. Sculimbrene Tetrahedron, 2012, 68, 9023-9028.
(13) "A Wet-lab Approach to Stereochemistry Using 31P NMR Spectroscopy" O.S. Fenton and B.R. Sculimbrene J. Chem. Ed. 2011, 88, 662-664 .
(12) "Synthesis of a D-Ala-D-Ala Peptide Isostere via Olefin Cross-metathesis and Evaluation of Vancomycin Binding" R.K. Quinn, A.L. Cianci, J.A. Beaudoin and B.R. Sculimbrene Bioorg. Med. Chem. Lett. 2010, 20, 4382-4385.
(11) "Efficient Catalyst Turnover in the Phosphitylation of Alcohols with Phosphoramidites" P.B. Brady, E.M. Morris, O.S. Fenton and B.R. Sculimbrene Tetrahedron Lett., 2009, 50, 975-978.
(10) "Lanthanide-Binding Tags with Unnatural Amino Acids: Sensitizing Tb(III) and Eu(III) Luminescnece at Longer Wavelengths." A.M. Reynolds, B.R. Sculimbrene, and B. Imperiali Bioconjugate Chem. 2008, 19, 588-591.
(9) "Lanthanide-Binding Tags as Luminescent Probes for Studying Proteins" B.R. Sculimbrene and B. Imperiali J. Am. Chem. Soc. 2006, 128, 7346-7352.
(8) "Streamlined synthesis of Phosphatidylinositol (PI), PI3P, PI3,5P2 , and Deoxygenated Analogues as Potential Biological Probes" Y.J. Xu, B.R. Sculimbrene, and S.J. Miller J. Org. Chem. 2006, 71, 4919-4928.
(7) "Rapid Combinatorial Screening of Peptide Libraries for the Selection of Lanthanide-Binding Tags (LBTs)" L.J. Martin, B.R. Sculimbrene, M. Nitz, and B. Imperiali QCS Comb. Sci. 2005, 24, 1149-1157.
(6) "Desymmetization of Glycerol Derivatives with Peptide-based Acylation Catalysts" C.A. Lewis, B.R. Sculimbrene, Y.J. Xu, and S.J. Miller Org. Lett. 2005, 7, 3021-3023.
(5) "Asymmetric Synthesis of Phosphatidyl-3-Phosphates with Saturated and Unsaturated Side Chains through Catalytic Asymmetric Phosphorylation." B.R. Sculimbrene, Y.J. Xu and S.J. Miller J. Am. Chem. Soc. 2004, 126, 13182-13183.
(4) "Nonenzymatic Peptide-based Catalytic Asymmetric Phosphorylation of Inositol Derviatives." B.R. Sculimbrene, A.J, Morgan and S.J. Miller Chem. Commun. 2003, 15, 1781-1785.
(3) "Enantiodivergence in Small-Molecule Catalysis of Asymmetric Phosphorylation: Concise Total Syntheses of the Enantiomeric D-myo-Inositol-1-phosphate and D-myo-Inositol-3-phosphate." B.R. Sculimbrene, A.J. Morgan and S.J. Miller J. Am. Chem. Soc. 2002, 124, 11653-11656.
(2) "Discovery of a Catalytic Asymmetric Phosphorylation through Selection of a Minimal Kinase Mimic." B.R. Sculimbrene and S.J. Miller J. Am. Chem. Soc. 2001, 123, 10125-10126.
(1) "Silatranyl-Nucleosides: Transition State Analogues for Phosphoryl Transfer Reactions" B.R. Sculimbrene, R.E. Decanio, B.W. Peterson, E.E. Muntel, and E.E. Fenlon Tetrahedron Lett. , 2001, 30, 4979-4982.
Patents:
(1) "Peptide as Kinase Mimic Catalysts for Asymmetric Phosphorylation in Synthesis of Phosphorylated Inositols and Cyclo-alkanols" B.R. Sculimbrene, S.J. Miller and A.J. Morgan PCT Int. Appl. WO 2003004141 A3, 2003.
Doctoral Dissertation:
(1) "Catalytic Asymmetric Phosphorylation: Concise Total Syntheses of Inositol Phosphates" B.R. Sculimbrene 2004.