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Chemistry & Chemical Biology / New Brunswick |
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Ralf Warmuth Associate Professor 1989 Diploma, Universität zu Köln, Germany 1992 Ph. D., Johann Wolfgang Goethe-Universität, Frankfurt am Main, Germany 1992-94 Postdoctoral researcher, University of Nottingham, U.K. 1994-97 Feodor Lynen fellow, University of California at Los Angeles |
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Research
Summary
Host-Guest Chemistry; Supramolecular Chemistry; Design and Synthesis of Molecular Containers; Inner Phase Chemistry and Catalysis; Reactive Intermediates; Strained Hydrocarbons; De Novo Design of Helical Peptides; Conformationally Constrained Amino Acids; Peptide-based Ion-Channels; Photochemical Triggers for Protein FoldingHost-Guest isolation of reactive intermediates: 1,2,4,6-cycloheptatetraene
The enantiomerization of 1,2,4,6-cycloheptatetraene (CHTE) in the inner phase of a chiral hemicarcerand. The enantiomerization of CHTE via the planar cycloheptatrienylidene (CHT) as the transition state is an important part of the phenylcarbene rearrangement. Recently, we generated CHTE photochemically in the inner phase of a chiral hemicarcerand, which prevented the dimerization of the highly strained guest. This allowed us to measure the exchange rate between the two diastereomeric CHTE hemicarceplexes (left and right structures) and to determine the enantiomerization barrier. Host-Guest isolation of reactive intermediates: o-benzyne
The photochemical generation of o-benzyne in the inner phase of a hemicarcerand (center). Photolysis of incarcerated benzocyclobutenedione yields o-benzyne and two molecules of CO, which escape the inner phase (bottom right bull eye). The surrounding hemicarcerand protected the highly strained o-benzyne from self-destruction, e.g. dimerization, and allowed us to characterize for the first time o-benzyne by liquid phase NMR spectroscopy. Partial 13C-NMR spectra of a fully 13C-labeled o-benzyne are shown in the bull eyes on the left side and in the upper right corner.Conformationally constrained peptides
A conformationally constrained lysine induces a single alpha helical turn in a short peptide.
Representative Publications
o-Benzyne: Strained Alkyne or a Cumulene?-NMR Characterization in a MolecularContainer. Ralf Warmuth, Angew. Chem. Int. Ed. Engl. 1997, 36, 1347-1350. pdf
First innermolecular Diels-Alder reaction of o-benzyne inside a molecular container compound. Ralf Warmuth, J. Chem. Soc., Chem. Commun., 1998, 59-60. pdf
The Inner Phase of Molecular Container Compounds as a Novel Reaction Environment.
Ralf Warmuth, J. Inclusion Phenomena and Molecular Recognition in Chemistry, 2000, 37, 1-38. pdf
1,2,4,6-Cycloheptatetraene: Room temperature stabilization inside a hemicarcerand.
Ralf Warmuth and Melissa A. Marvel, Angew. Chem. Int. Ed. Engl., 2000, 39, 1117-1119. pdf
Inner Phase Stabilization of Reactive Intermediates. Ralf Warmuth, Eur. J. Org. Chem., 2001, 423-437. pdf
Chemistry and Properties of Cycloheptatetraene Inside a Hemicarcerand. Ralf Warmuth and Melissa A. Marvel, Chem. Eur. J., 2001, 7, 1209-1220. pdf
Recent Highlights in Hemicarcerand Chemistry. Ralf Warmuth and Juyoung Yoon, Accounts of Chemical Research, 2001, 34, 95-105. pdf
Enantioselective synthesis of benzocyclic alpha, alpha-dialkyl-amino acids: New insight into the solvent dependent stereoselectivity of the TMS-CN addition to phenylglycinol derived imines. Ralf Warmuth, Tamara E. Munsch, Robert A. Stalker, Bing Li and Alicia Beatty, Tetrahedron., 2001, 57, 6383-6397. pdf
The Enantiomerization Barrier of 5-Methylcyclohepta-1,2,4,6-tetraene. Ralf Warmuth, J. Am. Chem. Soc., 2001, 123, 6955-6956. pdf
Rate Acceleration Through Dispersion Interactions: Insight into the Effect of a Hemicarcerand on the Transition State of Inner Phase Diazirine Decompositions. Ralf Warmuth, Jean-Luc Kerdelhue, Sigifredo Sanchez Carrera, Kevin J. Langenwalter, and Neil Brown. Angew. Chem. Int. Ed. Engl., 2002, 41, 96-99. pdf
Asymmetric Synthesis of two new Conformationally Constrained Lysine Derivatives. Ralf Warmuth, Tamara E. Munsch, Robert A. Stalker, Jacquelyn D. Tran, Xiaoping Nie, Alicia Beatty, and Christer Aakeroy, Tetrahedron, 2002, 58, 4837-4849. pdf
Chiral recognition by hemicarcerand-like host in aqueous solution. Harmit Singh and Ralf Warmuth, Tetrahedron, 2002, 58, 1257-1264. pdf
Mapping the Potential Energy Surface of the Tolylcarbene Rearrangement in the Inner Phase of a Hemicarcerand. Jean-Luc Kerdelhue, Kevin J. Langenwalter, Ralf Warmuth, J. Am. Chem. Soc., 2003, 125, 973-986. pdf
Temperature dependence of the kinetic isotope effect and tunneling contribution in the innermolecular reaction of phenylcarbene inside a hemicarcerand. Carly Kemmis and Ralf Warmuth, J. Supramol. Chem. 2003, 253 - 267.
Through-shell alkyl lithium additions and borane reductions. Ralf Warmuth, Emily F. Maverick, Carolyn, B. Knobler and Donald J. Cram, J. Org. Chem., 2003, 68, 2077-2088. pdf
The room-temperature stabilization of bicyclo[2.2.2]oct-1-ene and bicyclo[3.2.1]oct-1-ene. Paul Roach and Ralf Warmuth, Angew. Chem. Int. Ed. Engl., 2003, 42, 3039-3042. pdf
The Phenylnitrene Rearrangement in the Inner Phase of a Hemicarcerand. Ralf Warmuth and Slawomir Makowiec, J. Am. Chem. Soc., 2005, 127, 1084-1085. pdf
Fluorophenoxycarbene inside a hemicarcerand: a bottled singlet carbene. Xuejun Liu, Gaosheng Chu, Robert A. Moss, Ronald R. Sauers, and Ralf Warmuth, Angew. Chem. Int. Ed. Engl., 2005, 44, 1994-1997. pdf
A ’Through-Shell’ Binding Isotope Effect. Yong Liu and Ralf Warmuth, Angew. Chem. Int. Ed. Engl., 2005, 44, 7107-7110. pdf
One-Pot 18 Component Synthesis of an Octahedral Nanocontainer Molecule. Xuejun Liu, Yong Liu, Gina Li, Ralf Warmuth, Angew. Chem. Int. Ed. Engl., 2006, 45, 901-904. pdf