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Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings.
Beilstein J Org Chem 2019; 15:1552-1562BJ

Abstract

The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps.

Authors+Show Affiliations

Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Campus San Francisco, Universidad de Zaragoza, 50009 Zaragoza, Spain.Dipartimento di Scienze del Farmaco, University of Catania, V.le A. Doria 6, 95125 Catania, Italy.Dipartimento di Scienze del Farmaco, University of Catania, V.le A. Doria 6, 95125 Catania, Italy.Dipartimento di Chimica, Università di Pavia, Via Taramelli, 12, 27100, Pavia, Italy.Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Campus San Francisco, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain.Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Campus San Francisco, Universidad de Zaragoza, 50009 Zaragoza, Spain.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31354874

Citation

Pedrón, Manuel, et al. "Transient and Intermediate Carbocations in Ruthenium Tetroxide Oxidation of Saturated Rings." Beilstein Journal of Organic Chemistry, vol. 15, 2019, pp. 1552-1562.
Pedrón M, Legnani L, Chiacchio MA, et al. Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings. Beilstein J Org Chem. 2019;15:1552-1562.
Pedrón, M., Legnani, L., Chiacchio, M. A., Caramella, P., Tejero, T., & Merino, P. (2019). Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings. Beilstein Journal of Organic Chemistry, 15, pp. 1552-1562. doi:10.3762/bjoc.15.158.
Pedrón M, et al. Transient and Intermediate Carbocations in Ruthenium Tetroxide Oxidation of Saturated Rings. Beilstein J Org Chem. 2019;15:1552-1562. PubMed PMID: 31354874.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings. AU - Pedrón,Manuel, AU - Legnani,Laura, AU - Chiacchio,Maria-Assunta, AU - Caramella,Pierluigi, AU - Tejero,Tomás, AU - Merino,Pedro, Y1 - 2019/07/11/ PY - 2019/03/02/received PY - 2019/07/02/accepted PY - 2019/7/30/entrez PY - 2019/7/30/pubmed PY - 2019/7/30/medline KW - DFT KW - alkanes KW - carbocations KW - oxidations KW - ruthenium tetroxide SP - 1552 EP - 1562 JF - Beilstein journal of organic chemistry JO - Beilstein J Org Chem VL - 15 N2 - The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps. SN - 1860-5397 UR - https://www.unboundmedicine.com/medline/citation/31354874/Transient_and_intermediate_carbocations_in_ruthenium_tetroxide_oxidation_of_saturated_rings L2 - https://www.ncbi.nlm.nih.gov/pmc/articles/pmid/31354874/ DB - PRIME DP - Unbound Medicine ER -