Examining the vinyl moiety as a protecting group for hydroxyl (–OH) functionality under basic conditions

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

doi:10.1039/d0qo00202j

Cited by 28 publications

(15 citation statements)

References 71 publications

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“…The less reactive 3‐chloro‐6‐diethylamino‐1,2,4,5‐tetrazine 1 h reacted with an excess of benzyl vinyl ether in the presence of Et 3 N, producing pyridazine 2 h in 30% yield within 3 weeks (Table 1, entry 8). Triethylamine was used for benzyl vinyl ether protection from decomposition in the presence of 1 h [18i] . The resulting pyridazines can be easily isolated with standard protocols, so this synthetic path is totally suitable for the synthesis of electron donating group‐substituted pyridazines, which cannot be obtained from calcium carbide using a two‐chamber reactor.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

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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“…Vinyl ethers can be easily synthesized from solid CaC 2 , as was shown previously. [61][62][63][64][65][66][67] Although CaC 2 is traditionally produced from fossil coal, CaC 2 can also be produced in a carbon-neutral way without utilizing coal. [68] Moreover, utilizing fossil coal in organic synthesis can be perceived as a promising utility to coal by itself, contrary to using it as fuel.…”

Section: An In Silico Hammett Studymentioning

confidence: 99%

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

et al. 2022

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A tangible substituent effect may be perceived as a good feature in developing an organic reaction. This work demonstrates that, on the contrary, a zero-slope Hammet plot should be sought. The synthesis of isoxazoles by consecutive cycloaddition of nitrile oxides to vinyl ethers and alcohols elimination was studied computationally and experimentally. We performed a Hammett study in silico to demonstrate a negligible substituent effect (i. e., broad substrate scope) in the addition of benzyl vinyl ether to nitrile oxides. The modeling was performed at the ωB97X-V/def2-TZVP//PBE0-D4/def2-TZVP + SMD(benzene) level of theory within the RIJCOSX approximation. The experimental evaluation validated the computational model. A versatile methodology for synthesizing substituted isoxazolines and isoxazoles was proposed as the main result. We present this work as a successful example of how quantum chemical modeling can re-boost the classic Hammett approach to the optimization and design of organic synthetic methodologies. We anticipate further Hammett studies in silico, considering the current trend for data-driven chemical research.

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“…Thus, vinyl group was successfully used as a protecting group. [ 40 ] Moreover, acetaldehyde can be easily collected after devinylation. [ 41 ]…”

Section: A Map Of Calcium Carbide Synthetic Transformationsmentioning

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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Examining the vinyl moiety as a protecting group for hydroxyl (–OH) functionality under basic conditions

Abstract: A method for the protection and deprotection of alcohols via vinylation and devinylation reactions is proposed. Stability of the vinyl protecting group under various conditions is studied and synthetic applicability is demonstrated.

Cited by 28 publications

References 71 publications

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

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

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

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