Title: Associate Professor Organic Chemistry
Office: 205 Science and Engineering Building
Phone: (248) 370-2085
B.Sc. (Chemistry), University College Dublin (1992-1996)
Ph.D. Chemistry, University College Dublin (1996-2000) with Dr. Declan G. Gilheany.
Postdoctoral research, University of Glasgow (2002-2004) with Dr. David J. Procter.
Postdoctoral research, University of Pittsburgh (2004-2006) with Prof. Scott G. Nelson
Our group’s research is concerned with the development of efficient enantioselective and diastereoselective synthetic methods and their application in drug molecule and natural product synthesis. We also carry out extensive mechanistic studies of our new reactions, principally through NMR spectroscopy (e.g. 31P NMR and 1H NMR), to gain mechanistic insight, identify intermediates, and establish general patterns of reactivity. Much of our studies in recent years have involved the development of chiral organic nucleophile-catalyzed synthetic methods. Specifically, we have developed a number of chiral phosphine-catalyzed reactions of ketenes providing versatile methods for the asymmetric synthesis of biologically important molecules such as β-lactones (ketene dimers and saturated β-lactones) and β-lactams.
In 2012, we disclosed the first catalytic asymmetric heterodimerization of ketenes. This reaction was catalyzed by an alkaloid nucleophile (a quinine or quinidine derivative) to give a β-lactone ketene heterodimer product. One current avenue of intense research in our lab involves elaboration of our ketene heterodimer products to cancer therapeutic agents and complex molecules isolated from mycobacterium tuberculosis. We also have an interest in ylide chemistry (sulfoxonium and phosphonium ylides), organophosphorus chemistry (preparation and uses of phosphorus-containing compounds), as well as the development of new transition metal-catalyzed cross-coupling reactions. In the area of sulfoxonium ylide chemistry, we very recently published a modification of the Johnson-Corey-Chaykovsky reaction which facilitated a diastereoselective synthesis of g-lactones, through interception of a sulfoxonium ylide-derived betaine intermediate by a ketene molecule.
Kerrigan group research has been supported by the National Science Foundation since 2009 (2 awards: 2009-2012 and 2012-2015).
Current collaborators include Professor Arthur Bull (Oakland University: enzyme inhibition studies) and Professor Kraig A. Wheeler (Eastern Illinois University: X-ray crystallographic studies).
Note: Undergraduate co-authors are underlined.
M. Mondal, H.-J. Ho, N. J. Peraino, M. A. Gary, K. A. Wheeler, and N. J. Kerrigan. ‘Diastereoselective Reaction of Sulfoxonium Ylides, Aldehydes and Ketenes: An Approach to trans-gamma-Lactones’. J. Org. Chem. 2013, 78, 4587-4593.
P.-H. Wei, M. A.Gary, D. Nalla, G. D. Harzmann, A. A. Ibrahim, K. R. Dayak,N. J. Kerrigan. ‘Diastereoselective Formation of beta-hydroxyketones by the reduction of Ketene dimers.’ Tetrahedron Lett. 2013, 54, 932-935.
A. A. Ibrahim, D. Nalla, M. Van Raaphorst, N. J. Kerrigan. ‘Catalytic Asymmetric Heterodimerization of Ketenes.’ J. Am. Chem. Soc. 2012, 134, 2942-2945.
S. Chen, E. C. Salo, K. A. Wheeler, N. J. Kerrigan. ‘BINAPHANE-catalyzed asymmetric synthesis of trans-β-lactams from disubstituted ketenes and N-tosyl arylimines.’ Org. Lett. 2012, 14, 1784-1787.
N. J. Peraino, N. J. Kerrigan. ‘6'-Methoxy-(8S,9R)-Cinchonan-9-yl N-tert-butoxycarbonyl-2-pyrrolidinecarboxylate.’ Electronic Encyclopedia of Reagents for Organic Synthesis. 2012.
S. Chen, E. C. Salo, N. J. Kerrigan. ‘Tertiary amine and phosphine-catalyzed reactions of ketenes and α-halo ketones.’ Chapter 1.1.10, in Science of Synthesis Reference Library, Asymmetric Organocatalysis, Vol. 1, Lewis Base and Acid Catalysts; Edited by Benjamin List, Thieme: Stuttgart, 2012; Chapter 1.1.10, p 455-496.
M. Mondal, A. A. Ibrahim, K. A. Wheeler, N. J. Kerrigan. ‘Phosphine-catalyzed asymmetric synthesis of b-lactones from arylketoketenes and aromatic aldehydes.’ Org. Lett. 2010, 12, 1664-1667.
A. A. Ibrahim, P.-H. Wei, G. D. Harzmann, and N. J. Kerrigan. ‘Catalytic asymmetric homodimerization of ketoketenes.’ J. Org. Chem. 2010, 75, 7901-7904.
P.-H. Wei, A. A. Ibrahim, M. Mondal, D. Nalla, G. D. Harzmann, F. A. Tedeschi, K. A. Wheeler, and N. J. Kerrigan ‘Mechanistic studies of the phosphine-catalyzed homodimerization of ketoketenes.’ Tetrahedron Lett. 2010, 51, 6690-6694.
M. Mondal, N. J. Kerrigan. ‘Bradsher reaction.’ Chapter 4.5, Name Reactions for Carbocyclic Ring Formations. Edited by J. J. Li, Wiley & Sons: New Jersey, 2010.
N. J. Kerrigan. ‘Bergman Cyclization.’ Chapter 4.2, Name Reactions for Carbocyclic Ring Formations. Edited by J. J. Li, Wiley & Sons: New Jersey, 2010.
A. A. Ibrahim, S. M. Smith, S. Henson, N. J. Kerrigan. ‘Synthesis of 1,3-diketones through ring-opening of ketoketene dimer b-lactones.’ Tetrahedron Lett. 2009, 50, 6919-6922.
A. A. Ibrahim, G. D. Harzmann, N. J. Kerrigan. ‘Organocatalytic dimerization of ketoketenes.’ J. Org. Chem. 2009, 74, 1777-1780.
N. J. Kerrigan. Update to ‘Chromium(II) acetate.’ Electronic Encyclopedia of Reagents for Organic Synthesis 2008.
N. J. Kerrigan, C. J. Bungard, S. G. Nelson. ‘Pd(II)-catalyzed aliphatic Claisen rearrangements of acyclic allyl vinyl ethers.’Tetrahedron 2008, 64,6863-6869.
N. J. Kerrigan, H. Müller-Bunz, D. G. Gilheany. ‘Salen ligands derived from trans-1,2-dimethyl-1,2-cyclohexanediamine: preparation and application in oxo-chromium salen mediated asymmetric epoxidation of alkenes.’ J. Mol. Catal. A: Chemical2005, 227, 163-172.
N. J. Kerrigan, T. Upadhyay, D. J. Procter. ‘The samarium(II)-mediated intermolecular couplings of ketones and b-alkoxyacrylates: a short asymmetric synthesis of an antifungal g-butyrolactone.’ Tetrahedron Lett. 2004, 45, 9087-9090.
N. J. Kerrigan, P. C. Hutchison, T. D. Heightman, D. J. Procter. "Development of a solid-phase, asymmetric ‘resin-capture-release’ process: application of an ephedrine chiral resin in an approach to g-butyrolactones.' Organic and Biomolecular Chemistry 2004, 2, 2476-2482.
N. J. Kerrigan, E. C. Dunne, D. Cunningham, P. McArdle, K. Gilligan, D. G. Gilheany. ‘Studies in the preparation of novel P-chirogenic binaphthyl monophosphanes (MOPs).’ Tetrahedron Lett. 2003, 44, 8461-8465.
N. J. Kerrigan, P. C. Hutchison, T. D. Heightman, D. J. Procter. 'Application of an ephedrine chiral linker in a solid-phase, ‘asymmetric catch-release’ approach to g-butyrolactones.' Oral Presentation, ORGN 0334, Abstracts of 226th National Meeting of the American Chemical Society, New York, September, 2003.
N. J. Kerrigan, P. C. Hutchison, T. D. Heightman, D. J. Procter. Application of an ephedrine chiral linker in a solid-phase, ‘asymmetric catch-release’ approach to g-butyrolactones. Chem. Commun. 2003, 1402-1403.
N. J. Kerrigan, I. J. Langan, C. T. Dalton, A. M. Daly, C. Bousquet, D. G. Gilheany. ‘Asymmetric alkene epoxidation with chromium oxo salen complexes. Effect of added phosphoryl ligands.’ Tetrahedron Lett. 2002, 43, 2107-2110.
C. P. O’Mahony, E. M. McGarrigle, M. F. Renehan, K. M. Ryan, N. J. Kerrigan, C. Bousquet, D. G. Gilheany. ‘Asymmetric Alkene Epoxidation with Chromium Oxo Salen Complexes. A Systematic Study of Salen Ligand Substituents.’ Org. Lett. 2001, 3, 3435-3438.
N. J. Kerrigan, C. T. Dalton, C. Bousquet, D. G. Gilheany. ‘Ligand effects on chromium-catalyzed asymmetric alkene epoxidation.’ Poster presentation, ORGN 0733 Part 2, Abstracts of 219th National Meeting of the American Chemical Society, San Francisco, March 26, 2000.