2024-03-29T10:39:22Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/2206372021-12-27T16:49:36Zcom_10261_52707com_10261_5col_10261_52708
00925njm 22002777a 4500
dc
Pedrón, Manuel
author
Legnani, Laura
author
Chiacchio, Maria A.
author
Caramella, Pierluigi
author
Tejero, Tomás
author
Merino, Pedro
author
2019
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.
Beilstein Journal of Organic Chemistry 15: 1552–1562 (2019)
1860-5397
http://hdl.handle.net/10261/220637
10.3762/bjoc.15.158
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100010067
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/100008634
http://dx.doi.org/10.13039/501100004769
31354874
Alkanes
Ruthenium tetroxide
Carbocations
Oxidations
DFT
Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings