Polycyclic bridgehead acetals with enol functionality: one-pot assembly from aliphatic ketones and acetylene in KOH/DMSO suspension

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

doi:10.1016/j.tet.2016.06.010

Cited by 10 publications

(4 citation statements)

References 42 publications

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“…As an alternative to Favorskii reaction, ketones and acetylene can undergo a one-pot cascade cyclization to give 7-methylene-6,8-dioxabicyclo[3.2.1]octanes [ 145 , 146 , 147 , 148 , 149 , 150 ]. Under optimized conditions [ 145 , 146 ] a variety of bicyclic products were obtained from dialkyl [ 145 ] and aryl alkyl [ 146 , 147 ] ketones ( Scheme 60 ).…”

Section: Acetylene In Organic Synthesismentioning

confidence: 99%

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Acetylene in Organic Synthesis: Recent Progress and New Uses

et al. 2018

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Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.

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Section: Acetylene In Organic Synthesismentioning

confidence: 99%

“…A proposed mechanism for this reaction involves the following cascade transformations [ 145 ]. A superbase-promoted addition of the initial ketone to acetylene yields an intermediate 2-propenyl ketone, which undergoes prototropic isomerization into 1-propenyl ketone A .…”

Section: Acetylene In Organic Synthesismentioning

confidence: 99%

Acetylene in Organic Synthesis: Recent Progress and New Uses

et al. 2018

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“…A characteristic feature of this system is its autostabilization (self-tuning): its basicity is maintained at one level due to the absorption of water (if it is formed in the reaction) by the solid phase (KOH); the concentration of KOH in the liquid phase is small (∼0.04 M for pure DMSO) and is replenished in the case of consumption from the solid phase, i.e., is automatically maintained constant, which promotes a gentle flow of chemical processes. In the syntheses of methylene-6,8-dioxabicyclo[3.2.1]octanes from 1,5-diketones, 13 aliphatic and alicyclic ketones, 14 and acetylene, the KOH/DMSO system is even more effective than the superbasic media based on potassium tert-butoxide.…”

Section: Introductionmentioning

confidence: 99%

Transition-Metal-Free C-Vinylation of Ketones with Acetylenes: A Quantum-Chemical Rationalization of Similarities and Differences in Catalysis by Superbases MOH/DMSO and tBuOM/DMSO (M = Na, K)

et al. 2018

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Transition-metal-free C-vinylation of acetone with phenylacetylene catalyzed by superbases MOH/DMSO and tBuOM/DMSO (M = Na, K) has been theoretically evaluated in the B3LYP/6-311++G**//B3LYP/6-31+G* approach to rationalize similarities and differences in activity of the above catalytic systems. The close solvate surroundings of sodium and potassium tert-butoxides have been studied. Formation of tBuOM· nDMSO complexes and their structure and thermodynamic stability are discussed in comparison with similar complexes of alkali-metal hydroxides MOH· nDMSO. Activation barriers of the title reaction in the presence of tBuOM· nDMSO complexes are found to be less than those with MOH· nDMSO complexes participating.

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“…Recently, we disclosed the one-pot transition-metal-free diastereoselective assembly of densely substituted bicyclic vinyl ethers 1 , 7-methylene-6,8-dioxabicyclo[3.2.1]octanes, from two molecules of acetylene and two molecules of ketones in the KOH/DMSO superbase system (Scheme A) …”

mentioning

confidence: 99%