Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene

Кобычев, В. Б.; Orel, Vladimir B.; Zankov, D. V.; Vitkovskaya, N. M.; Трофимов, Б. А.

doi:10.1007/s11172-017-2006-2

Cited by 2 publications

(1 citation statement)

References 16 publications

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“…Among all the studied reactions 1 to 9 , the highest activation barriers were found for nucleophilic additions to the triple bond. The PENTA GAS model predicts these activation energies in the range of 26 to 20 kcal/mol, which is consistent with their rate‐determining role in the formation of 6,8‐dioxabicyclo[3.2.1]octanes, cyclopentenols, and furans . Notably, the O ‐vinylation does not occur during the interaction of enolate ion with the acetylene molecule.…”

Section: Resultssupporting

confidence: 70%

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Vitkovskaya

Orel

Кобычев

et al. 2020

Int J of Quantum Chemistry

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The mechanisms of fundamental base‐promoted acetylene reactions, namely, nucleophilic addition to the triple C ≡ C bond (vinylation) and nucleophilic addition of acetylenic carbanion to a carbonyl group (ethynylation), are addressed using three models of different complexity—pentasolvate, monosolvate, and anionic—which describe the catalytic superbasic systems MOH(OBut)/DMSO (suspensions of alkali hydroxides or tert‐butoxides in dimethyl sulfoxide). The above acetylene reactions and sequential transformations of reagents arranged by the superbasic center are modeled within the framework of the most complete pentasolvate model, in which the superbase is represented by the KOH·5DMSO (KOBut·5DMSO) complexes. We have developed approaches to the construction of simplified models (monosolvate and anionic) to describe transformations in complex systems. The mechanisms of cascade assemblies of 6,8‐dioxabicyclo[3.2.1]octanes, cyclopentenones, and furan cycles from ketones and acetylenes in the superbasic environment are investigated using a uniform B2PLYP/6‐311+G**//B3LYP/6‐31+G* approach, and the energy profiles of these different carbo‐ and heterocycles are analyzed.

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Section: Resultssupporting

confidence: 70%

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Vitkovskaya

Orel

Кобычев

et al. 2020

Int J of Quantum Chemistry

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show abstract

Quantum chemical comparison of ethynylation and C-vinylation routes in superbase catalyzed reaction of acetylenes with imines

Orel

Vitkovskaya

Absalyamov

et al. 2019

Mendeleev Communications

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Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene

Cited by 2 publications

References 16 publications

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Quantum chemical comparison of ethynylation and C-vinylation routes in superbase catalyzed reaction of acetylenes with imines

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Quantum chemical modeling of superbase-catalyzed reactions of acetophenone and methyl mesityl ketone with acetylene

Cited by 2 publications

References 16 publications

Quantum‐chemical models of KOH(KOBut)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Quantum‐chemical models of KOH(KOBut)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Quantum chemical comparison of ethynylation and C-vinylation routes in superbase catalyzed reaction of acetylenes with imines

Contact Info

Product

Resources

About

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions

Quantum‐chemical models of KOH(KOBu^t)/DMSO superbasic systems and mechanisms of base‐promoted acetylene reactions