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Nonlinear Temperature Behavior of Product Ratios in Selection Processes^†^‡

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Dr. Detlef Heller

Max-Planck-Gesellschaft Arbeitsgruppe “Asymmetrische Katalyse” an der Universität, Buchbinderstrasse 5/6, D-18055 Rostock (Germany) Fax: Int. code +(381)4669324 e-mail: [email protected]

Max-Planck-Gesellschaft Arbeitsgruppe “Asymmetrische Katalyse” an der Universität Buchbinderstrasse 5/6, D-18055 Rostock (Germany) Fax: Int. code +(381)4669324 e-mail: [email protected]Search for more papers by this author

Dr. Helmut Buschmann,

Dr. Helmut Buschmann

Grünenthal GmbH Aachen, Forschungszentrum, Zieglerstrasse 6, D-52078 Aachen (Germany)

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Prof. Dr. Hans-Dieter Scharf,

Prof. Dr. Hans-Dieter Scharf

Institut für Organische Chemie der Technischen Hochschule Professor-Pirlet-Strasse 1, D-52056 Aachen (Germany)

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Dr. Detlef Heller,

Corresponding Author

Dr. Detlef Heller

Max-Planck-Gesellschaft Arbeitsgruppe “Asymmetrische Katalyse” an der Universität, Buchbinderstrasse 5/6, D-18055 Rostock (Germany) Fax: Int. code +(381)4669324 e-mail: [email protected]

Dr. Helmut Buschmann,

Dr. Helmut Buschmann

Grünenthal GmbH Aachen, Forschungszentrum, Zieglerstrasse 6, D-52078 Aachen (Germany)

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Prof. Dr. Hans-Dieter Scharf,

Prof. Dr. Hans-Dieter Scharf

Institut für Organische Chemie der Technischen Hochschule Professor-Pirlet-Strasse 1, D-52056 Aachen (Germany)

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First published: September 6, 1996

https://doi.org/10.1002/anie.199618521

Citations: 35

^†

The authors thank Prof. D. Haberland for stimulating discussions and Prof. J. Ridd, London, for communicating his results. This work was supported by Prof. R. Selke, the Max-Planck-Gesellschaft, and the Fonds der Chemischen Industrie.

^‡

Dedicated to Professor Ivar Ugi on the occasion of his 65th birthday

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Abstract

Displaced intermolecular and intramolecular equilibria, which lead to a nonlinear change in the concentration ratios of intermediates, are possibly the cause for the experimentally long-known nonlinear temperature dependence of logarithmic product ratios in selection processes (isoinversion principle). This interpretation takes into account a change in dominance of differences in the activation enthalpy and entropy for the overall selection process, as well as a change in the rate-determining step with variation of the temperature.

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Volume35, Issue16

September 6, 1996

Pages 1852-1854

Nonlinear Temperature Behavior of Product Ratios in Selection Processes^†^‡

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Nonlinear Temperature Behavior of Product Ratios in Selection Processes^†^‡