Research Projects: Neural Networks and Machine Learning in Chemistry
Computer-aided Discovery of Novel Chemical Reactions
According to a systematic classification of about 80000 reactions, most organic reactions can be described by a linear (i.e. nucleophilic / electrophilic attack, substitution, elimnination) or cyclic (pericyclic reactions) sequence of electron pushing arrows. However, there is a third class of reactions that we coined "coarctate reations". Coarctate mechanisms include at least one atom (or a sequence of atoms) at which two bonds are made and two bonds are broken simultaneously. A prominent example is the epoxidation of alkenes with peroxocarboxylic acids.
Because of their intricate mechanisms, coarctate reactions are less exhaustively investigated than pericyclic or linear reactions. Based on their common reaction principle, we predicted a number of new reactions which have been realized in the laboratory. Among them are particularly useful synthetic methods such as coarctate cyclizations.
Key Publications:
Reaction planning: computer-aided discovery of a novel elimination reaction.
R. Herges, C. Hoock, Science 1992, 255, 711-713.
DOI
Coarctate transition states: the discovery of a reaction principle.
R. Herges, J. Chem. Inf. Comput. Sci. 1994, 34, 91-102.
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Coarctate and Pseudocoarctate Reactions: Stereochemical Rules
R. Herges, J. Org. Chem. 2015, 80, 11869-11876.
DOI
Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization: Pseudocoarctate versus Pericyclic Reactivity
D. Kimball, B. David, R. Herges, M. M. Haley, J. Am. Chem. Soc. 2002, 124, 1572-1573.
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Literature:
- Organizing Principle of Complex Reactions and Theory of Coarctate Transition States.
R. Herges, Angew. Chem. 1994, 106, 261; Angew. Chem. Int. Ed. Engl. 1994, 33, 255-276.
- Coarctate Transition States: The Discovery of a Reaction Principle.
J. Chem. Inf. Comput. Sci. 1994, 43, 91-106.
- A Spontaneous Fragmentation - From the Criegee Zwitterion to the Coarctate Möbius Aromaticity
Berger, C. Bresler, U. Dilger, D. Geuenich, R. Herges*, H. Röttele, G. Schröder*, Angew. Chem.1998, 110,1951-1954; Angew. Chem. Int. Ed. Engl. 1998, 37, 1850-1853
- Formaldehyd-O-oxid und Colchicine: ein eleganter Zugang zu Allocolchicinen
U. Dilger, B. Franz, H. Röttele, G. Schröder*, R. Herges*, J. Prakt. Chem. 1998, 340, 468-471
- Ethynylogization of a Coarctate Fragmentation
R. Herges, D. Geuenich, G. Bucher, C. Tönshoff, Chemistry 2000, 6, 1224-1228.
- Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization: Pseudocoarctate versus Pericyclic Reactivity
D. B. Kimball, R. Herges, M. M. Haley, J. Am. Chem. Soc. 2002, 124, 1572-1573.
- Deciphering the Mechanistic Dichotomy in the Cyclization of 1-(2-Ethynylphenyl)-3,3-dialkyltriazenes: Competition between Pericyclic and Pseudocoarctate Pathways
D. B. Kimball, T. J. R. Weakley, R. Herges, M. M. Haley, J. Am. Chem. Soc. 2002, 124, 13463-13473.
- Experimental and Theoretical Investigation of the Coarctate Cyclization of (2-Ethynylphenyl)phenyldiazenes
L. D. Shirtcliff, T. J. R. Weakley, M. M. Haley, F. Koehler, R. Herges, J. Org. Chem. 2004, 69, 6979-6985.
- Biscyclization Reactions in Butadiyne- and Ethyne-Linked Triazenes and Diazenes: Concerted versus Stepwise Coarctate Cyclizations
L. D. Shirtcliff, A. G. Hayes, M. M. Haley, F. Koehler, K. Hess, R. Herges, J. Am. Chem. Soc. 2006, 128, 9711-9721.
- CuCl-Induced Formation and Migration of Isoindazolyl Carbenoids
L. D. Shirtcliff, M. M. Haley, R. Herges, J. Org. Chem. 2007, 72, 2411-2418.
- Computational analysis of the dual reactivity of conjugated hetero-'ene-ene-yne' systems
S. P. McClintock, L. D. Shirtcliff, R. Herges, M. M. Haley, Abstracts of Papers, 235th ACS National Meeting, New Orleans, LA, United States, April 6-10, 2008, ORGN-409.
- Computational Analysis on the Dual Reactivity of Conjugated "Ene-Ene-Yne" Systems
S. P. McClintock, L. D. Shirtcliff, R. Herges, M. M. Haley, J. Org. Chem. 2008, 73, 8755-8762.
- Synthesis of α-Ketoester- and α-Hydroxyester-Substituted Isoindazoles via the Thermodynamic Coarctate Cyclization of Ester-Terminated Azo-Ene-Yne Systems
S. P. McClintock, N. Forster, R. Herges, M. M. Haley, J. Org. Chem. 2009, 74, 6631-6636.
- Coarctate versus Pericyclic Reactivity in Naphthalene-Fused Azo-Ene-Ynes: Synthesis of Benzocinnolines and Benzoisoindazoles
S. P. McClintock, L. N. Zakharov, R. Herges, M. M. Haley, Chem. Eur. J. 2011, 17, 6798-6806.
- Phenanthrene-Fused Azo-ene-ynes: Synthesis of Dibenzo[f,h]cinnoline and Dibenzo[e,g]isoindazole Derivatives
B. S. Young, F. Köhler, R. Herges, M. M. Haley, J. Org. Chem. 2011, 76, 8483-8487.
