Efficient labeling of organic molecules using13C elemental carbon: universal access to13C2-labeled synthetic building blocks, polymers and pharmaceuticals

Ledovskaya, Maria S.; Voronin, V. V.; Rodygin, Konstantin S.; Ananikov, Valentine P.

doi:10.1039/c9qo01357a

Cited by 35 publications

(29 citation statements)

References 113 publications

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“…The nucleophilic addition proceeds under superbasic conditions in good yields without the use of gaseous acetylene and can be safely carried out in a laboratory. Labeled compounds with deuterium [21] and carbon 13 C [22] incorporation can also be obtained that increase applications in further transformations: polymerization [23], Heck-like reactions [24], cycloaddition [25,26], and many others. Here, we expand the scope of applications of vinyl derivatives and demonstrate that molecular hydrogen can be successfully added to functionalized vinyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

Sustainable Hydrogenation of Vinyl Derivatives Using Pd/C Catalysts

Mironenko¹,

Saybulina²,

Степанова³

et al. 2021

Catalysts

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The hydrogenation of unsaturated double bonds with molecular hydrogen is an efficient atom-economic approach to the production of a wide range of fine chemicals. In contrast to a number of reducing reagents typically involved in organic synthesis, hydrogenation with H2 is much more sustainable since it does not produce wastes (i.e., reducing reagent residues). However, its full sustainable potential may be achieved only in the case of easily separable catalysts and high reaction selectivity. In this work, various Pd/C catalysts were used for the liquid-phase hydrogenation of O-, S-, and N-vinyl derivatives with molecular hydrogen under mild reaction conditions (room temperature, pressure of 1 MPa). Complete conversion and high hydrogenation selectivity (>99%) were achieved by adjusting the type of Pd/C catalyst. Thus, the proposed procedure can be used as a sustainable method for vinyl group transformation by hydrogenation reactions. The discovery of the stability of active vinyl functional groups conjugated with heteroatoms (O, S, and N) under hydrogenation conditions over Pd/C catalysts opens the way for many useful transformations.

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Section: Introductionmentioning

confidence: 99%

Sustainable Hydrogenation of Vinyl Derivatives Using Pd/C Catalysts

Mironenko¹,

Saybulina²,

Степанова³

et al. 2021

Catalysts

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“…Using this methodology, we successfully synthesized a range of pyrazoles and their labeled derivatives, 4,5‐dideuteropyrazoles, from calcium carbide [19a] . Additionally, we started an investigation of CaC 2 reactivity in Diels‐Alder reactions, obtaining 3,6‐dichloropyridazine‐4,5‐ 13 C 2 in quantitative yield [19b] …”

Section: Resultsmentioning

confidence: 99%

“…All chemicals were purchased from Sigma Aldrich, Alfa Aesar and Acros Organics in reagent grade or better quality and used without further purification. Tetrazines 1 a – c , j were synthesized by procedures reported previously [19b,28] . D 3 ‐vinyl ether was synthesized by a previously reported procedure [20] .…”

Section: Methodsmentioning

confidence: 99%

One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

Ledovskaya

Polynski

Ananikov

2021

Chemistry An Asian Journal

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Acetylene surrogates are efficient tools in modern organic chemistry with largely unexplored potential in the construction of heterocyclic cores. Two novel synthetic paths to 3,6‐disubstituted pyridazines were proposed using readily available acetylene surrogates through flexible C2 unit installation procedures in a common reaction space mode (one‐pot) and distributed reaction space mode (two‐chamber): (1) an interaction of 1,2,4,5‐tetrazine and its acceptor‐functionalized derivatives with a CaC2−H2O mixture performed in a two‐chamber reactor led to the corresponding pyridazines in quantitative yields; (2) [4+2] cycloaddition of 1,2,4,5‐tetrazines to benzyl vinyl ether can be considered a universal synthetic path to a wide range of pyridazines. Replacing water with D2O and vinyl ether with its trideuterated analog in the developed procedures, a range of 4,5‐dideuteropyridazines of 95–99% deuteration degree was synthesized for the first time. Quantum chemical modeling allowed to quantify the substituent effect in both synthetic pathways.

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“…A versatile approach for 13 C 2 ‐labeling of organic molecules by using calcium carbide‐ 13 C 2 has been proposed. [ 53 ] Ca 13 C 2 , synthesized from calcium and 13 C elemental carbon, is used as in situ source of 13 C 2 ‐acetylene, the universal 13 C 2 unit for atom‐economic organic transformations. This protocol opens access to a variety of 13 C 2 ‐labeled compounds and in many cases, it is easy to implement in a two‐chamber reactor (Figure 1B).…”

Section: Cost‐efficient and Eco‐friendly 2h And 13c Labelingmentioning

confidence: 99%

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

et al. 2020

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Acetylene is a key building block for organic chemistry and potentially can be involved in a diverse range of synthetic transformations. However, critical analysis of practical considerations showed that application of gaseous acetylene in regular synthetic labs encounters a number of difficulties. Safety limitations due to flammable and explosive nature of gaseous acetylene and requirements for specialized high‐pressure equipment impose serious drawbacks. Typical reaction conditions involve excess of gaseous reactant, which is simply released to the atmosphere at the end of the reaction, thus generating waste and causing contamination. Calcium carbide brings a new green and sustainable wave into powerful alkyne transformations and significantly expands the repertoire of traditional acetylene chemistry. The novel trend of using calcium carbide instead of gaseous acetylene is synthetically beneficial and opens a novel reactivity for the C≡C unit. This review highlights recent advances in carbide chemistry, demonstrates its advantages and prospects in term of green synthetic approach.

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Efficient labeling of organic molecules using¹³C elemental carbon: universal access to¹³C₂-labeled synthetic building blocks, polymers and pharmaceuticals

Abstract: Synthetic methodology enabled by 13C-elemental carbon is reported. Calcium carbide Ca13C2 was applied to introduce a universal 13C2 unit in the synthesis of labeled alkynes, O,S,N-vinyl derivatives, labeled polymers and 13C2-pyridazine drug core.

Cited by 35 publications

References 113 publications

Sustainable Hydrogenation of Vinyl Derivatives Using Pd/C Catalysts

Sustainable Hydrogenation of Vinyl Derivatives Using Pd/C Catalysts

One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

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