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 Research

The Chemistry Department NMR facility supports university researchers with three spectrometers: 300 MHz, 400 MHz and 500 MHz.

Below is a sampling of recent publications that have utilized the department facilities.

Sigman Research Group

Asymmetric Catalysis, Organometallic Chemistry and Organic Synthesis

Chen, Z. M., Hilton, M. J., and Sigman, M. S. (2016) Palladium-Catalyzed Enantioselective Redox-Relay Heck Arylation of 1,1-Disubstituted Homoallylic Alcohols. J. Am. Chem. Soc.138, 11461–11464.

An enantioselective redox-relay oxidative Heck arylation product was confirmed via H and 13C NMR spectroscopy recorded at 300 MHz and 500 MHz.

McCammant, M. S., Shigeta, T., and Sigman, M. S. (2016) Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids. Org. Lett.18, 1792–1795.

A palladium catalyzed reaction of terminal alkenes that resulted in good stereo- and regioselectivity of the products which was confirmed via 1H and 13C NMR spectroscopy recorded at 400 MHz and 500 MHz.

Niemeyer, Z. L., Milo, A., Hickey, D. P., and Sigman, M. S. (2016) Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes. Nat. Chem.8, 610–617.

This study helped to shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands and their reaction mechanisms. The phosphine forms were characterized by 1H, 31P and 13C NMR spectroscopy recorded at 500 MHz. Additionally, a model was determined utilizing the NMR chemical shift value of a phosphine selenide.

Patel, H. H., and Sigman, M. S. (2016) Enantioselective Palladium-Catalyzed Alkenylation of Trisubstituted Alkenols to Form Allylic Quaternary Centers. J. Am. Chem. Soc.138, 14226–14229.

This report describes the generation of remote allylic quaternary stereocenters and the products were confirmed by 1H and 13C NMR spectroscopy recorded at 300 MHz, 400 MHz, and 500 MHz.

Race, N. J., Schwalm, C., Nakamuro, T., and Sigman, M. S. (2016) Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols. J. Am. Chem. Soc. jacs.6b11486.

Enantioselective intermolecular coupling products were characterized by 1H and 13C NMR spectroscopy recorded at 400 MHz and 500 MHz.

Santiago, C. B., Milo, A., and Sigman, M. S. (2016) Developing a Modern Approach to Account for Steric Effects in Hammett-Type Correlations. J. Am. Chem. Soc.138, 13424–13430.

The products of several palladium catalyzed reactions were characterized by 1H and 13C NMR spectroscopy recorded at 400 MHz and 500 MHz.

Yamamoto, E., Hilton, M. J., Orlandi, M., Saini, V., Toste, F. D., and Sigman, M. S. (2016) Development and Analysis of a Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer. J. Am. Chem. Soc. jacs.6b11367.

Novel enantioselective products of palladium catalysis were characterized by 1H and 13C NMR spectroscopy recorded at 300 MHz and 500 MHz

Bess, E. N., Guptill, D. M., Davies, H. M. L., and Sigman, M. S. (2015) Using IR vibrations to quantitatively describe and predict site-selectivity in multivariate Rh-catalyzed C-H functionalization. Chem. Sci.6, 3057–3062.

Products resulting in selective functionalization were characterized by 1H and 13C NMR spectroscopy recorded at 400 MHz.

Hickey, D. P., Milton, R. D., Chen, D., Sigman, M. S., and Minteer, S. D. (2015) TEMPO-Modified Linear Poly(ethylenimine) for Immobilization-Enhanced Electrocatalytic Oxidation of Alcohols. ACS Catal.5, 5519–5524.

Covalently immobilized oxidation catalyst products were characterized by 1H NMR spectroscopy recorded at 400 MHz.

Hickey, D. P., Schiedler, D. A., Matanovic, I., Doan, P. V., Atanassov, P., Minteer, S. D., and Sigman, M. S. (2015) Predicting Electrocatalytic Properties: Modeling Structure-Activity Relationships of Nitroxyl Radicals. J. Am. Chem. Soc.137, 16179–16186.

Electrocatalystical oxidation by stable nitroxyl radical containing compounds was characterized by 1H and 13C NMR spectroscopy recorded at 300 MHz, 400 MHz, and 500 MHz.

Hilton, M. J., Cheng, B., Buckley, B. R., Xu, L., Wiest, O., and Sigman, M. S. (2015) Relative reactivity of alkenyl alcohols in the palladium-catalyzed redox-relay Heck reaction. Tetrahedron71, 6513–6518.

Products from advanced alkenyl alcohol catalysis by palladium were characterized by 1H and 13C NMR spectroscopy recorded at 300 MHz and 500 MHz.

McCammant, M. S., and Sigman, M. S. (2015) Development and investigation of a site selective palladium-catalyzed 1,4-difunctionalization of isoprene using pyridine–oxazoline ligands. Chem. Sci.6, 1355–1361.

The palladium catalyzed reaction leading to complex isomeric product mixtures was confirmed with 1H and 13C NMR spectroscopy recorded at 400 MHz and 500 MHz.

Patel, H. H., and Sigman, M. S. (2015) Palladium-Catalyzed Enantioselective Heck Alkenylation of Acyclic Alkenols Using a Redox-Relay Strategy. J. Am. Chem. Soc.137, 3462–3465.

Highly enantioselective intermolecular Heck reactions were characterized by 1H and 13C NMR spectroscopy recorded at 300 MHz, 400 MHz, and 500 MHz.

Saini, V., O’dair, M., and Sigman, M. S. (2015) Synthesis of highly functionalized tri- and tetrasubstituted alkenes via Pd-catalyzed 1,2-hydrovinylation of terminal 1,3-dienes. J. Am. Chem. Soc.137, 608–611.

New efficient methods for organic synthesis were confirmed by 1H and 13C NMR spectroscopy recorded at 300 MHz, 400 MHz, and 500 MHz.

Zhang, C., Santiago, C. B., Crawford, J. M., and Sigman, M. S. (2015) Enantioselective Dehydrogenative Heck Arylations of Trisubstituted Alkenes with Indoles to Construct Quaternary Stereocenters. J. Am. Chem. Soc.137, 15668–15671.

An enantioselective arylation reaction had its products characterized by 1H and 13C NMR spectroscopy recorded at 400 MHz and 500 MHz.

Zhang, C., Santiago, C. B., Kou, L., and Sigman, M. S. (2015) Alkenyl Carbonyl Derivatives in Enantioselective Redox Relay Heck Reactions: Accessing α,β-Unsaturated Systems. J. Am. Chem. Soc.137, 7290–7293.

A site-selective palladium catalyzed arylation had its products characterized by 1H and 13C NMR spectroscopy recorded at 300 MHz and 500 MHz

 

 

 

Last Updated: 2/7/17