Full Cleavage of C≡C Bond in Electron-Deficient Alkynes via Reaction with Ethylenediamine

Vasilevsky, S. F.; Davydova, Maria P.; Mamatyuk, V. I.; Tsvetkov, Nikolay P.; Hughes, Audrey; Baranov, Denis S.; Alabugin, Igor V.

doi:10.1071/ch17026

Cited by 14 publications

(8 citation statements)

References 28 publications

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“…However, conditions are harsher than in the case of α-acetylenic ketones. The fragmentation proceeds most effectively in refluxing pyridine with the 50-fold excess of the nucleophile (Scheme 39) [128].…”

Section: Alkynes As Carbonyl Surrogates In the Synthesis Of Aldol mentioning

confidence: 99%

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

et al. 2019

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The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these “obvious” traits, there are other more subtle, often concealed aspects of this functional group’s appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, “classic carbonyl chemistry” can be accessed through alkynes, and new transformations can be engineered by unmasking the hidden carbonyl nature of alkynes. The goal of this review is to illustrate the advantages of using alkynes as an entry point to carbonyl reactions while highlighting reports from the literature where, sometimes without full appreciation, the concept of using alkynes as a hidden entry into carbonyl chemistry has been applied.

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Section: Alkynes As Carbonyl Surrogates In the Synthesis Of Aldol mentioning

confidence: 99%

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

et al. 2019

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“…2 Moreover, they are known as important intermediates in organic transformations. 3−5 There are numerous methods for the synthesis of 2-imidazolines, 2-oxazolines, and 2-thiazolines from different precursors such as carboxylic acids, 6,7 aldehydes, 8−11 amides, 12 thioamides, 13 esters, 14,15 aziridines, 16−19 anthraquinone, 20 carbene complex, 21 and nitriles 22−24 under various reaction conditions and a variety of homogeneous and heterogeneous catalysts. In spite of the potential utility of the above-mentioned procedures for the synthesis of these nitrogen-containing heterocycles, some of these methods suffer from one or more disadvantages, such as harsh reaction conditions (strong acidic conditions), use of stoichiometric amounts of catalysts, use of complex and expensive reagents and toxic solvents, long reaction times, and low yields of products.…”

Section: Introductionmentioning

confidence: 99%

Cu(II) immobilized on Fe$_{3}$O$_{4}$@Agarose nanomagnetic catalyst functionalized with ethanolamine phosphate--salicylaldehyde Schiff base: a magnetically reusable nanocatalyst for preparation of 2-substituted imidazolines, oxazolines, and thiazolines

Zarei¹,

Akhlaghinia²

2018

Turk J Chem

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Herein we synthesized Cu(II) immobilized on Fe 3 O 4 @Agarose functionalized with ethanolamine phosphatesalicylaldehyde Schiff base (Fe 3 O 4 @Agarose/SAEPH 2 /Cu(II)) as a new and cost-effective nanomagnetic catalyst. The nanomagnetic catalyst was characterized by FT-IR, XRD, VSM, SEM-EDX, TEM, TGA, and ICP techniques and it was found that the particles were about 9-25 nm in size and spherical with entrapment of the Fe 3 O 4 particles in the hollow pore structure of the agarose. The prepared nanomagnetic catalyst showed excellent activity for preparation of 2-substituted imidazolines, oxazolines, and thiazolines. The catalyst is easy to prepare and exhibits higher catalytic activity than some commercially available copper sources. More importantly, this nanomagnetic catalyst can be easily recovered by using a permanent magnet and reused for at least seven cycles without significant deactivation.

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“…This was followed by the formation of methyl aryl ketones and the corresponding 2substituted imidazoline derivatives. This case was of theoretical interest as an example of how the complete cleavage of a strong C≡C bond could be achieved under mild conditions through the action of ethylenediamine ( Figure 13) [15].…”

Section: Chemical Propertiesmentioning

confidence: 99%

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

Vasilevsky¹,

Stepanov²

2020

REFFIT

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In addition to the reported synthetic routes for the acetylene derivatives of quinones, a detailed analysis of the fundamental chemical, physicochemical, and biological properties of this class of compounds is presented herein. The advantages of Pd- and Cu-catalyzed cross-coupling of terminal alkynes with iodarenes via the Sonogashira reaction to produce new acetylenylquinones with predetermined properties are examined. Here, combining quinoid and acetylene residues into one molecule gives the resulting compounds chemical specificity, as demonstrated by several reported examples of non-trivial transformations. In particular, the presence of the quinoid cycle significantly increases the electrophilicity of the triple bond and determines the range of transformation possibilities. Moreover, acetylenylquinones have heightened sensitivity to both external (such as the reaction temperature and the nature of the solvent) and internal (e.g., the structure of substituents in the nucleus and the acetylene fragment) factors. For example, regioselective cleavage of a strong triple bond under the action of amines is possible in the absence of a metal catalyst. Peri-substituted acetylenyl-9,10-anthraquinones are most suited for the synthetic route because of the proximity of the acetylene and carbonyl groups. Mechanisms of reactions of selective alkynylquinones are described.

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Full Cleavage of C≡C Bond in Electron-Deficient Alkynes via Reaction with Ethylenediamine

Cited by 14 publications

References 28 publications

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Cu(II) immobilized on Fe$_{3}$O$_{4}$@Agarose nanomagnetic catalyst functionalized with ethanolamine phosphate--salicylaldehyde Schiff base: a magnetically reusable nanocatalyst for preparation of 2-substituted imidazolines, oxazolines, and thiazolines

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

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