Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

Schmidt, Elena Yu.; Bidusenko, Ivan A.; Cherimichkina, Natalia A.; Трофимов, Б. А.

doi:10.3998/ark.5550190.p009.302

Arkivoc

2015

DOI: 10.3998/ark.5550190.p009.302

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Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

Elena Yu. Schmidt¹,

Ivan A. Bidusenko²,

Natalia A. Cherimichkina³

et al.

Abstract: The condition-controlled switch between the bicyclic ketals, 7-methylene-6,8-dioxabicyclo[3.2.1]octanes and 3-acyl-2-cyclopenten-1-ols formation during the 2:2 selfassembly of acetylenes with ketones in the presence of the KOH/DMSO suspension at 30-70 o C has been developed. The selectivity reaches ca. 100% for bicyclic ketals and 67% for cyclopentenols. Both reactions are diastereoselective.

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Cited by 4 publications

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Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

Vitkovskaya

Orel

Кобычев

et al. 2018

Int J of Quantum Chemistry

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Most of the strategies for the synthesis of 6,8‐dioxabicyclo[3.2.1]octanes (BCO) and cyclopentenols (CP), which show high biological and pharmaceutical activity, are multistage and/or require hardly accessible starting materials and catalysts. The general method for BCO and CP preparation in a single preparative stage from two simple reagents, ketones and acetylene, under the action of an available super‐basic catalytic system KOH/DMSO becomes promising for the development of general approaches to the design of these classes of biologically active compounds. The mechanism of competing reactions yielding both 7‐methylene‐6.8‐dioxabicyclo[3.2.1]‐octanes and functionalized cyclopentenoles from their common intermediate 1,5‐diketones and acetylene in the KOH/DMSO superbasic media is investigated using the B2PLYP/6‐311++G**//B3LYP/6‐31+G* calculations with particular attention to the diastereoselectivity aspects of individual stages.

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Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

Vitkovskaya

Orel

Кобычев

et al. 2018

Int J of Quantum Chemistry

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

et al. 2017

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Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

Cited by 4 publications

References 23 publications

Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

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

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

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Expedient nonclassical reaction of acetylenes with ketones: controlling the switch between bicyclic ketals and cyclopentenols formation

Cited by 4 publications

References 23 publications

Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

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

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

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Product

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