Vinylation of Alcohols, Thiols, and Nitrogen Compounds Using a Stoichiometric Amount of In Situ Generated Acetylene
Maria S. Ledovskaya, Vladimir V. Voronin, Anna A. Reznichenko, Ekaterina A. Reznichenko
Organics · pp. 5–5 · Published 8 Feb 2025
10.3390/org6010005Abstract
In this work, we developed a highly efficient and versatile environmentally benign methodology for the vinylation of a broad scope of substances, including alcohols, thiols, and nitrogen compounds. The key advantage of the proposed method is the use of calcium carbide as a robust acetylene source in a stoichiometric ratio to the substrates. Lacking the requirement of acetylene excess, the developed protocol is safe, highly economic, and limits waste production. The procedure allows for a large variety of O-,S-,N-vinyl compounds to be synthesized in up to quantitative yields. Our methodology is scalable, allowing us to obtain vinyl derivatives in Gram-scale quantities. We also demonstrated the significant synthetic value of our approach by performing a label-economic synthesis of 13C2-labeled vinyl derivatives using calcium carbide-13C2. In our well-optimized process, the conversion of Ca13C2 reached 89%.
References (85)
- 1 Oesch, 2021, N-vinyl compounds: Studies on metabolism, genotoxicity, carcinogenicity [DOI]
- 2 Ledovskaya, 2018, Methods for the synthesis of O-, S- and N-vinyl derivatives [DOI]
- 3 Silva, V.L.M., and Silva, A.M.S. (2022). Revisiting the Chemistry of Vinylpyrazoles: Properties, Synthesis, and Reactivity. Molecules, 27. [DOI]
- 4 Xiao, 2024, Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: Modular access to structurally complex α-amino ketones [DOI]
- 5 Er, 2024, Synthesis of Degradable Homopolymer, Gradient and Block Copolymers, and Self-Assembly via RAFT Polymerization of 4,4-Dimethyl-2-methylene-1,3-dioxolan-5-one [DOI]
- 6 Jiang, 2017, Rhodium(ii)-catalyzed intermolecular [3 + 2] annulation of N-vinyl indoles with N-tosyl-1,2,3-triazoles via an aza-vinyl Rh carbene [DOI]
- 7 Teator, 2019, Catalyst-controlled stereoselective cationic polymerization of vinyl ethers [DOI]
- 8 Sugihara, 2022, From controlled radical polymerization of vinyl ether to polymerization-induced self-assembly [DOI]
- 9 Ledovskaya, 2021, One-Pot and Two-Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D-Labeled Derivatives [DOI]
- 10 Ledovskaya, 2020, Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium-Labeled Pyrazole Synthesis [DOI]
- 11 Fragis, 2021, Aldehyde to Ketone Homologation Enabled by Improved Access to Thioalkyl Phosphonium Salts [DOI]
- 12 Lou, 2020, Transition-metal mediated carbon–sulfur bond activation and transformations: An update [DOI]
- 13 Schobert, 2014, Production of Acetylene and Acetylene-based Chemicals from Coal [DOI]
- 14 Voronin, V.V., Ledovskaya, M.S., Bogachenkov, A.S., Rodygin, K.S., and Ananikov, V.P. (2018). Acetylene in Organic Synthesis: Recent Progress and New Uses. Molecules, 23. [DOI]
- 15 Mu, 2024, Synthesis of N-vinylcarbazole from acetylene by a continuous high-pressure liquid-phase process with inherent safety [DOI]
- 16 Mondal, 2021, Synthesis of vinyl sulfides and thioethers via a hydrothiolation reaction of 4-hydroxydithiocoumarins and arylacetylenes/styrenes [DOI]
- 17 Trofimov, 2015, Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene [DOI]
- 18 Gusarova, 2013, Highly efficient atom economical “green chemistry” synthesis of vinyl sulfides from thiols and acetylene in water [DOI]
- 19 Shmidt, 2013, Improved method for the synthesis of 1-vinylindole [DOI]
- 20 Rusakov, 2008, Synthesis and conformational analysis of furfuryl vinyl ethers [DOI]
- 21 Trofimov, 2007, Acetylene: New prospects of classical reactions [DOI]
- 22 Trofimov, 2002, Acetylene and its Derivatives in Reactions with Nucleophiles: Recent Advances and Current Trends [DOI]
- 23 Zyk, 2003, Methods for the synthesis of vinyl sulfides [DOI]
- 24 Kimura, 2017, Iridium-Catalyzed Vinylation of Carbazole Derivatives with Vinyl Acetate [DOI]
- 25 Queffelec, 2008, Synthesis of P,N-Heterocycles from ω-Amino-H-Phosphinates: Conformationally Restricted α-Amino Acid Analogs [DOI]
- 26 Guillerm, 2004, Inactivation of S-adenosylhomocysteine hydrolase with haloethyl and dihalocyclopropyl esters derived from homoadenosine-6′-carboxylic acid [DOI]
- 27 McKeon, 1972, The palladium (II) catalyzed vinyl interchange reaction—II [DOI]
- 28 Gao, 2022, Base-Promoted Synthesis of Vinyl Sulfides from Sulfonium Triflates [DOI]
- 29 Politanskaya, 2022, Synthetic approaches to fluorinated derivatives of 4-(vinylthio)pyridine [DOI]
- 30 Sitte, 2021, Phosphine-Catalyzed Vinylation at Low Acetylene Pressure [DOI]
- 31 Zhao, 2023, PhI(OAc)2-Mediated Regioselective Hydrothiolation of Allenamides with Thiophenol via a Radical Process: Synthesis of Vinyl Sulfides [DOI]
- 32 Beletskaya, 2022, Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges [DOI]
- 33 Nie, 2022, Synthesis of Non-Terminal Alkenyl Ethers, Alkenyl Sulfides, and N-Vinylazoles from Arylaldehydes or Diarylketones, DMSO and O, S, N-Nucleophiles [DOI]
- 34 Bolshan, 2008, Enamide Synthesis by Copper-Catalyzed Cross-Coupling of Amides and Potassium Alkenyltrifluoroborate Salts [DOI]
- 35 Blouin, 2001, A New Method for the Preparation of Aryl Vinyl Ethers [DOI]
- 36 Matake, 2016, Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO) [DOI]
- 37 Rattanangkool, 2016, An Atom-Economic Approach for Vinylation of Indoles and Phenols Using Calcium Carbide as Acetylene Surrogate [DOI]
- 38 Voronin, 2020, Examining the vinyl moiety as a protecting group for hydroxyl (–OH) functionality under basic conditions [DOI]
- 39 Parshina, 2019, Towards C1 chemistry: Methanol vinylation by CaC2 in water in the presence of potassium or sodium carbonates [DOI]
- 40 Ledovskaya, 2019, Direct Synthesis of Deuterium-Labeled O-, S-, N-Vinyl Derivatives from Calcium Carbide [DOI]
- 41 Teong, 2017, Vinylation of Aryl Ether (Lignin β-O-4 Linkage) and Epoxides with Calcium Carbide through C−O Bond Cleavage [DOI]
- 42 Teong, 2017, Direct vinylation of natural alcohols and derivatives with calcium carbide [DOI]
- 43 Ledovskaya, 2023, Calcium carbide: Highly potent solid reagent for the construction of heterocycles [DOI]
- 44 Rodygin, 2021, Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability [DOI]
- 45 Ma, 2021, Synthesis of Diarylethynes from Aryldiazonium Salts by Using Calcium Carbide as an Alkyne Source in a Deep Eutectic Solvent [DOI]
- 46 Liu, 2021, Synthesis of 1,3-Diynes Using Calcium Carbide as an Alkyne Source [DOI]
- 47 Liu, 2020, Synthesis of Bis(trimethylsilyl)acetylene (BTMSA) by Direct Reaction of CaC2 with N-(trimethylsilyl)imidazole [DOI]
- 48 Gao, 2020, Synthesis of aromatic terminal allenes and aliphatic terminal alkynes from hydrazones using calcium carbide as an acetylene source [DOI]
- 49 Gao, 2019, Direct Synthesis of 1-Arylprop-1-ynes with Calcium Carbide as an Acetylene Source [DOI]
- 50 Teong, 2016, Copper catalysed alkynylation of tertiary amines with CaC2via sp3 C–H activation [DOI]
- 51 Wang, 2024, Highly Stereoselective Synthesis of 2-Acyl-3-sulfonamidobut-2-enoates Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene [DOI]
- 52 Yu, 2013, Acetylide Ion (C22−) as a Synthon To Link Electrophiles and Nucleophiles: A Simple Method for Enaminone Synthesis [DOI]
- 53 Gao, 2020, Direct Synthesis of Propen-2-yl Sulfones through Cascade Reactions Using Calcium Carbide as an Alkyne Source [DOI]
- 54 Ledovskaya, 2023, New Reactions of Acetylene Generated in Two-Chamber Reactor [DOI]
- 55 Scharnagel, 2020, Acetylene as a Dicarbene Equivalent for Gold(I) Catalysis: Total Synthesis of Waitziacuminone in One Step [DOI]
- 56 Shabalin, 2020, Calcium Carbide as Acetylene Source in Cascade Assemblies of Hydroxypyrrolines and 3H-Pyrroles from Ketoximes [DOI]
- 57 Kaewchangwat, 2015, Direct synthesis of aryl substituted pyrroles from calcium carbide: An underestimated chemical feedstock [DOI]
- 58 Voronin, 2021, Cycloaddition Reactions of in situ Generated C2D2 in Dioxane: Efficient Synthetic Approach to D2-Labeled Nitrogen Heterocycles [DOI]
- 59 Voronin, 2018, [3 + 2]-Cycloaddition of in Situ Generated Nitrile Imines and Acetylene for Assembling of 1,3-Disubstituted Pyrazoles with Quantitative Deuterium Labeling [DOI]
- 60 Yu, 2017, One-Pot Synthesis of Spirocyclic or Fused Pyrazoles from Cyclic Ketones: Calcium Carbide as the Carbon Source in Ring Expansion [DOI]
- 61 Yu, 2016, Calcium carbide as the acetylide source: Transition-metal-free synthesis of substituted pyrazoles via [1,5]-sigmatropic rearrangements [DOI]
- 62 Liu, 2023, Constructing 5-Methyl-2,4-diaryl-1H-imidazoles Using Calcium Carbide as Alkyne Source via A3-Coupling Cyclization [DOI]
- 63 Gonda, 2010, Efficient synthesis of deuterated 1,2,3-triazoles [DOI]
- 64 Ledovskaya, 2018, Calcium-mediated one-pot preparation of isoxazoles with deuterium incorporation [DOI]
- 65 Hosseini, 2019, Synthesis of Exclusively 4-Substituted β-Lactams through the Kinugasa Reaction Utilizing Calcium Carbide [DOI]
- 66 Voronin, 2023, 1,2,4-Triazines and Calcium Carbide in the Catalyst-Free Synthesis of 2,3,6-Trisubstituted Pyridines and Their D-, 13C-, and Doubly D2-13C2-Labeled Analogues [DOI]
- 67 Liao, 2023, One-Pot Three-Component Synthesis of 4-Arylpyrimidin-2-amines Using Solid Calcium Carbide as a Surrogate of Gaseous Acetylene [DOI]
- 68 Fu, 2018, Direct Synthesis of 2-Methylbenzofurans from Calcium Carbide and Salicylaldehyde p-Tosylhydrazones [DOI]
- 69 Wang, 2024, Construction of 3-Methyl-2-Substituted Benzo[b]furans and 3-Methyl-2-Substituted Benzo[b]thiophenes Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene [DOI]
- 70 You, 2024, One-step construction of indolo[2,1-a]isoquinolines using solid calcium carbide as an alternative to gaseous acetylene [DOI]
- 71 Wen, 2024, One-Pot Three-Component Construction of (Z)-3-Benzylidene-2-(quinolin-8-yl)isoindolin-1-ones Through C(sp2)−H Bond Activation Using Calcium Carbide as a Solid Alkyne Source [DOI]
- 72 Wang, 2024, Construction of 2-Methylindoles Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene [DOI]
- 73 Liu, 2024, One-Step Construction of 9,10-Diarylphenanthrenes Using Solid Calcium Carbide as an Alternative of Gaseous Acetylene [DOI]
- 74 Ledovskaya, 2024, The Use of Calcium Carbide for Cyclopentenone Ring Construction [DOI]
- 75 Zhang, 2022, Three-Component One-Pot Construction of 2-Aryl-4H-benzo[4,5]thiazolo[3,2-a]pyrimidines Using Solid Calcium Carbide as a Surrogate of Gaseous Acetylene [DOI]
- 76 Liu, 2021, Copper-Catalyzed Construction of Benzo[4,5]imidazo[2,1-a]isoquinolines Using Calcium Carbide as a Solid Alkyne Source [DOI]
- 77 Zimmerman, 2020, Designing for a green chemistry future [DOI]
- 78 Wink, 2024, Recent Progress in Turning Waste into Catalysts for Green Syntheses [DOI]
- 79 Sheldon, 2022, Metrics of green chemistry: Waste minimization [DOI]
- 80 Graells, 2021, Synthesis and assessment of waste-to-resource routes for circular economy [DOI]
- 81 Ghisellini, 2016, A review on circular economy: The expected transition to a balanced interplay of environmental and economic systems [DOI]
- 82 Werner, 2017, A solid acetylene reagent with enhanced reactivity: Fluoride-mediated functionalization of alcohols and phenols [DOI]
- 83 Ledovskaya, 2020, Efficient labeling of organic molecules using 13C elemental carbon: Universal access to 13С2-labeled synthetic building blocks, polymers and pharmaceuticals [DOI]
- 84 Ledovskaya, 2023, Calcium Carbide: From Elemental Carbon to Isotope-Economic Synthesis of 13C2-Labeled Heterocycles [DOI]
- 85 Kutskaya, 2022, Negligible Substituent Effect as Key to Synthetic Versatility: A Computational-Experimental Study of Vinyl Ethers Addition to Nitrile Oxides [DOI]
Cited by 6
M. S. Ledovskaya, V. V. Voronin · Russian Journal of General Chemistry · 2025
Anna A. Reznichenko, Vladimir V. Voronin, Maria S. Ledovskaya · Russian Journal of General Chemistry · 2025
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