Direct N- and C-vinylation with trimethoxyvinylsilane

Arsenyan, Pavel; Petrenko, Alla; Paegle, Edgars; Belyakov, Sergey

doi:10.1016/j.mencom.2011.11.011

Cited by 13 publications

(7 citation statements)

References 22 publications

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“…Cross-coupling reactions, catalyzed by copper [ 12 ] and iron [ 13 ], or palladium complexes [ 14 ], require a partner: trimethyloxyvinylsilane [ 15 ], potassium vinyltrifluoroborate [ 16 ], or vinyl halide [ 17 ] ( Scheme 1 , route b). Another non-atom economic strategy, elimination, is based on a two-step sequence, which is carried out under basic conditions ( Scheme 1 , route c).…”

Section: Introductionmentioning

confidence: 99%

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

2018

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We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed.

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Section: Introductionmentioning

confidence: 99%

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

2018

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“…Therefore, a robust synthesis of vinyl pyrimidines was needed. When we started our work, there was only a few reports of vinylation methods applied to pyrimidine nucleobases: N(1) alkylation followed by elimination; Chan‐Lam coupling using trimethoxyvinyl silane as the vinyl source, along with tetrabutyl ammonium fluoride (TBAF) and a stoichiometric amount of Cu(II); and nucleophilic attack of TMS‐protected thymine on vinyl acetate in the presence of trimethylsilyl trifluoromethane sulfonate (TMSOTf) . In our hands, the preparation of N(1) vinyl thymine 10a following these reported procedures failed (Scheme ).…”

Section: Synthesis Of Nucleoside Analogues Via Annulation Reactionsmentioning

confidence: 99%

Nucleoside Analogues: Synthesis from Strained Rings

Racine

Vuilleumier

Waser

2016

Israel Journal of Chemistry

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Nucleoside analogues are widely employed as bioactive compounds against cancer and viral infections. Consequently, it is important to develop efficient synthetic methods to access them with high efficiency and structural diversity. Herein, we present a full account of our work on the synthesis of nucleoside analogues via annulations of donor acceptor aminocyclopropanes and aminocyclobutanes. Thymine-and uracil-derived diester cyclopropanes were accessed from the corresponding nucleobases via vinylation and rhodium-catalyzed cyclopropanation, and were then used in (3+2) annulations with aldehydes, ketones and enol ethers.The obtained analogues could be transformed into important hydroxymethyl derivatives. Thymine and fluoro-uracil derived diester cyclobutanes obtained from the nucleobases via vinylation and (2+2) cycloaddition could also be used in a (4+2) annulation with aldehydes. Finally, purine-derived diester cyclopropanes could be accessed using the condensation of nucleobases with chloromethyl ethylidene malonates, but annulation reactions with this class of substrates was not successful.

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“…[11] Calcium carbide has similarly been used in the generation of vinyl thioesters from Svinylated thiophenols [12] as well as vinyl alcohols from O-vinylated aliphatic alcohols. Current methods for preparing N-vinylindole involve the metal-catalyzed reaction between an indole and coupling partner [20] such as trimethoxyvinylsilane, [21] vinyl bromide, [22] vinyl acetate [23] and ethylene, [24,25] (Scheme 1, left side). Moreover, it is a core structure for numerous natural products and biologically active compounds.…”

Section: Introductionmentioning

confidence: 99%

“…[16] On the other hand, aryl vinyl ethers serve as i) valuable intermediates in various reactions, [17] ii) precursors for polymeric materials, [18] and iii) as phenolic protecting groups [19] in organic synthesis. Current methods for preparing N-vinylindole involve the metal-catalyzed reaction between an indole and coupling partner [20] such as trimethoxyvinylsilane, [21] vinyl bromide, [22] vinyl acetate [23] and ethylene, [24,25] (Scheme 1, left side). An alternative method for N-vinylation of indoles involves the use of 1,2-dichloroethane in the presence of phase transfer catalyst.…”

Section: Introductionmentioning

confidence: 99%

An Atom‐Economic Approach for Vinylation of Indoles and Phenols Using Calcium Carbide as Acetylene Surrogate

et al. 2016

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An efficient N‐vinylation of indoles and O‐vinylation of phenols to give N‐vinyl indoles and phenyl vinyl ethers is reported. The vinylated products can be produced in satisfactory to excellent yields (65–92 %) upon treatment of indoles or phenols with calcium carbide in wet solvents in a standard laboratory setup. Key features of this reaction include the use of calcium carbide as a safe and inexpensive slow released acetylene source for N‐ and O‐vinylation under simple reaction conditions without the need for metal catalyst or halogenated substrates.

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Direct N- and C-vinylation with trimethoxyvinylsilane

Cited by 13 publications

References 22 publications

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

Nucleoside Analogues: Synthesis from Strained Rings

An Atom‐Economic Approach for Vinylation of Indoles and Phenols Using Calcium Carbide as Acetylene Surrogate

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