Conformational Flexibility of Fused Tetracenedione Propellers Obtained from One-Pot Reductive Dimerization of Acetylenic Quinones

Vasilevsky, S. F.; Baranov, Denis S.; Mamatyuk, V. I.; Fadeev, Dmitry S.; Gatilov, Yuri V.; Stepanov, A. A.; Vasilieva, Nadezhda V.; Alabugin, Igor V.

doi:10.1021/jo502543b

Cited by 16 publications

(8 citation statements)

References 84 publications

(41 reference statements)

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“…A particularly interesting process observed in these systems is reductive dimerization of such quinones into tetracene diones as displayed in Scheme 21 [72]. The mechanism for this transformation is still unclear.…”

Section: Vinyl Ether Generation From Alkynesmentioning

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: Vinyl Ether Generation From Alkynesmentioning

confidence: 99%

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

et al. 2019

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“…The propargyl ether substrates were assembled in one‐pot transformations from aryl aldehydes or aryl bromides (Scheme ). Oxidative workup with DDQ or MnO 2 could provide new polyaromatic ketones, albeit in varying yields (Scheme , entries 1–3), whereas treatment with TFA gave rise to the destannylated hydrocarbon derivatives (entries 4 and 5 in Scheme ). In particular, the pyrene precursor was transformed by the latter approach into a phenyl‐substituted “olympicene” 19…”

Section: Figurementioning

confidence: 86%

“…Oxidative workup with DDQ or MnO 2 could provide new polyaromatic ketones,a lbeit in varying yields (Scheme 3, entries 1-3), [17] whereas treatment with TFAg ave rise to the destannylated hydrocarbon derivatives (entries 4a nd 5i nS cheme 3). When the reaction mixture was treated with iodine before TFA, iodobenzanthrene 9 was isolated in moderate yield.…”

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confidence: 99%

Radical Alkyne peri‐Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene

et al. 2018

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“…On the contrary, 5-exo-dig cyclization into condensed pyrazoles was observed between the donor substituents in the aryllalkyne ragment and the OAc substituent at nucleus position 40. Carbocyclization, which is the reductive dimerization of acetylenyl-9,10-anthraquinones, is described in [21]. Here, the reaction of the alkynes 1a-c with guanidine was carried out in boiling n-butanol and resulted in the formation of O-5-exo-dig-and N-6-exo-dig-products 2 and 3, respectively.…”

Section: Chemical Propertiesmentioning

confidence: 99%

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

Vasilevsky¹,

Stepanov²

2020

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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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Conformational Flexibility of Fused Tetracenedione Propellers Obtained from One-Pot Reductive Dimerization of Acetylenic Quinones

Cited by 16 publications

References 84 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

Radical Alkyne peri‐Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene

Fundamental and Applied Aspects of the Chemistry of Acetylenylquinones

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