Theoretical investigation of the role of formaldehyde dimers in the Prins reaction

Kupova, Olga Yu.; Вакулин, И. В.; Талипов, Р. Ф.; Morozkin, Nikolay D.; Talipova, G. R.

doi:10.1007/s11144-013-0590-1

Cited by 8 publications

(2 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The optimized (PBE-D3/def2-SVP) transition state structure in the presence of the p -toluenesulfonate anion shows the electrophilic carbon approaching both carbon atoms of the olefin moiety, resembling a nonclassical “onium” ion ( TS-1 , Figure D). Furthermore, consistent with the report by Kupova, , the bond distance between the benzylic carbon and the remote oxygen was found to be 4.95 Å, ruling out any possibility of concerted cyclization. This arrangement suggests a stepwise operating pathway, where the benzylic carbocation intermediate rotates freely, leading to the observed cis / trans scrambling (Figure C).…”

mentioning

confidence: 99%

The Catalytic Asymmetric Intermolecular Prins Reaction

2021

View full text Add to dashboard Cite

Despite their significant potential, catalytic asymmetric reactions of olefins with formaldehyde are rare and metal-free approaches have not been previously disclosed. Here we describe an enantioselective intermolecular Prins reaction of styrenes and paraformaldehyde to form 1,3-dioxanes, using confined imino-imidodiphosphate ( i IDP) Brønsted acid catalysts. Isotope labeling experiments and computations suggest a concerted, highly asynchronous addition of an acid-activated formaldehyde oligomer to the olefin. The enantioenriched 1,3-dioxanes can be transformed into the corresponding optically active 1,3-diols, which are valuable synthetic building blocks.

show abstract

mentioning

confidence: 99%

The Catalytic Asymmetric Intermolecular Prins Reaction

2021

View full text Add to dashboard Cite

show abstract

“…Next, geometry found in RM1, corresponding to energy maximum on PES, was used in TS search procedure by iterative approximation method [25], which ended on MP2/6-31G(d,p) approach. Based on the established transition state, the activation energy of the process is found.…”

Section: Identification Of Transition Statementioning

confidence: 99%

Interaction of the transition state of the Claisen rearrangement with surface of carbon nanotubes to predict catalytic activity

Vakulin,

Talipov,

Fattakhov

et al. 2024

Preprint

View full text Add to dashboard Cite

The possibility of using the transition state shape selectivity concept for control of selectivity of reaction was previously demonstrated by us using the example of 1,3-dioxanes formation by Prins reaction. The extension of the applied approach to other reactions is of theoretical and practical interest. Considering that the main channel for the formation of 1,3-dioxanes by Prins reaction is realized through a cyclic transition state, it is primarily interesting to study the applicability of the above approach to other reactions also proceeding through a cyclic transition state: Claisen rearrangement, Diels-Alder reaction, etc. The aim of our work was to study the interaction of the frozen transition state of Claisen rearrangement with the surface of nanotubes of various structures to predict their catalytic activity. Claisen rearrangement of allylphenyl ether was chosen as a model reaction, and carbon nanotubes with different diameters were chosen as a porous materials. The calculated dependence of the stabilization energy on the nanotube diameter has an extreme character with pronounced maxima at a diameter of 10.2–10.4 Å. The obtained results allow to predict the catalytic activity of nanotubes with a diameter of 10-11 Å in Claisen rearrangement of allylphenyl ether.

show abstract