Regioselective and solvent-free arylation of β-nitrostyrenes with mono- and dialkyl anilines

Ranjbari, Mohammad Amin; Tavakol, Hossein; Manoukian, Meghmik

doi:10.1007/s11164-020-04294-6

Cited by 10 publications

(12 citation statements)

References 41 publications

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“…Thus, for example, when indole is treated with 4-methoxy-β-nitrostyrene, C3-alkylated indole is exclusively obtained in 92% yield. [54] The addition reactions at the N1 center are rare. Is it possible to make N-alkylation the main or even the only reaction direction?…”

Section: Indoles and Purinesmentioning

confidence: 99%

“…It has been well documented that among three nucleophilic centers (N1, C2, C3) the C3‐position of an indole is the most preferred site in reactions with electrophiles. Thus, for example, when indole is treated with 4‐methoxy‐β‐nitrostyrene, C3‐alkylated indole is exclusively obtained in 92% yield [54] . The addition reactions at the N1 center are rare.…”

Section: Indoles and Purinesmentioning

confidence: 99%

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Weak Nucleophiles in the Aza‐Michael Reaction

Rulev

2023

Adv Synth Catal

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The 1,4‐conjugated addition of nitrogen centered nucleophiles to electron‐deficient alkenes is one of the most significant and widely used reactions in modern synthetic organic chemistry. To date, various protocols for the aza‐Michael reaction have been developed. However, these reports mainly focus on the use of strong Michael donors. In recent years, the conjugate addition of weak nitrogen nucleophiles to various Michael acceptors gained increasing popularity. Impressive progress in this area has been achieved by the use of more efficient catalyst systems. This review aims to provide a critical analysis of the results obtained in reactions of weak nucleophiles (azoles, pyrroles, indoles, carbamates, purines, amides, hydrazides, uraciles etc) with electron‐deficient alkenes which were reported over the past twelve years.

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Section: Indoles and Purinesmentioning

confidence: 99%

Section: Indoles and Purinesmentioning

confidence: 99%

Weak Nucleophiles in the Aza‐Michael Reaction

Rulev

2023

Adv Synth Catal

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“…The same eutectic mixture was also employed to perform the acylation of electron-rich arenes using acid chlorides or anhydrides as acylating reagents; this is also recyclable up to five times ( Table 6 , entry 3) [ 113 ]. Finally, catalytic amounts of the ChCl:ZnCl 2 (1:2) mixture (10 mol%) were employed in the solvent-free reaction between mono- or dialkylated anilines and β-nitrostyrenes, yielding the corresponding alkylated products in good yields and excellent regioselectivity towards the para-substituted adducts ( Figure 38 , Table 6 , entry 4) [ 114 ].…”

Section: Miscellaneousmentioning

confidence: 99%

Deep Eutectic Solvents as à-la-Carte Medium for Transition-Metal-Catalyzed Organic Processes

Marset

Guillena

2022

Molecules

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Our society is facing a tremendous challenge to become more sustainable in every sphere of life. Regarding the chemical industry, one of the most significant issues to be addressed is the use of volatile organic compounds (VOCs) as solvents because they are petrol-derived and most of them are toxic and flammable. Among the possible solutions, deep eutectic solvents (DESs) have emerged as sustainable alternatives to VOCs in organic catalyzed transformations and other fields. The advantages of these new reaction media are not only related to their more benign physical and chemical properties and, for most of them, their renewable sources but also due to the possibility of being recycled after their use, increasing the sustainability of the catalyzed process in which they are involved. However, their use as media in catalytic transformations introduces new challenges regarding the compatibility and activity of known catalysts. Therefore, designed catalysts and “à-la-carte” DESs systems have been developed to overcome this problem, to maximize the reaction outcomes and to allow the recyclability of the catalyst/media system. Over the last decade, the popularity of these solvents has steadily increased, with several examples of efficient metal-catalyzed organic transformations, showing the efficiency of the catalysts/DES system, compared to the related transformations carried out in VOCs. Additionally, due to the inherent properties of the DES, unknown transformations can be carried out using the appropriated catalyst/DES system. All these examples of sustainable catalytic processes are compiled in this review.

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“…In fact, α-cyano phosphonate was not produced in any of the mentioned reactions. Therefore, after several successful studies of this group on the synthetic utility of BNSs and their derivatives [42][43][44], we aimed to prepare ACPs via a simple and nonexpensive method. In this report, an attempt has been made to synthesize the ACP derivatives using deep eutectic solvents (DESs) as a green catalyst.…”

mentioning

confidence: 99%

“…As the first step of the optimization experiments, various catalysts (20 mol percents), including organic catalyst, metal salts, choline chloride, and different DESs were employed (entries 1-9 of Table 1) in addition to the catalystfree conditions. DESs were chosen because of their high performances in catalyzing various reactions, including our previous studies related to the reactions of β-nitrostyrene [42,44]. The reactions without catalyst and using paratoluenesulfonic acid or SnCl2 as a catalyst showed zero or negligible yields (entries 1-3).…”

mentioning

confidence: 99%

Solvent-Free Synthesis of α-Cyanophosphonates from β-Nitrostyrenes by Using a Deep-Eutectic Solvent Catalyst

Tavakol,

Shi,

Shamsaddinimotlagh

et al. 2024

Synlett

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New α-Cyanophosphonates, which are useful reagents for Horner-Wittig reaction, were synthesized in a solvent-free condition, using choline chloride-zinc chloride deep eutectic solvent (DES) as a catalyst. This work is only the second report on the synthesis of these compounds. In the previous report, diethyltrimethylsilylphosphite was used as a reagent and TiCl4 as a catalyst while in this study, both employed reagent and catalyst (triphenyl phosphine and choline chloride-zinc chloride DES) are cheaper, more available and less harmful than the previous work. Moreover, the reaction involves an interesting cascade reaction between β-nitrostyrenes and two equivalents of triphenylphosphite led to the desired product as a new synthetic route. These compounds can be used in the pharmaceutical and agricultural industries, in addition to their synthetic applications in the preparation of α,β-unsaturated nitriles. The reactions were completed using 20 mol% of DES at 80 °C in 6 hours. 10 different β-nitrostyrenes were synthesized in 55-87% yield after purification. β-nitrostyrenes containing electron-donating groups showed higher yields. The reaction was failed when aliphatic and heteroaromatic nitroalkenes and β-nitrostyrenes with electron-withdrawing substituent were employed. Finally, three plausible mechanistic routes were proposed for the reaction, starting from the nucleophilic addition of triphenylphosphite to α-carbon, nitrogen and oxygen atoms.

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Regioselective and solvent-free arylation of β-nitrostyrenes with mono- and dialkyl anilines

Cited by 10 publications

References 41 publications

Weak Nucleophiles in the Aza‐Michael Reaction

Weak Nucleophiles in the Aza‐Michael Reaction

Deep Eutectic Solvents as à-la-Carte Medium for Transition-Metal-Catalyzed Organic Processes

Solvent-Free Synthesis of α-Cyanophosphonates from β-Nitrostyrenes by Using a Deep-Eutectic Solvent Catalyst

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Regioselective and solvent-free arylation of β-nitrostyrenes with mono- and dialkyl anilines

Cited by 10 publications

References 41 publications

Weak Nucleophiles in the Aza‐Michael Reaction

Weak Nucleophiles in the Aza‐Michael Reaction

Deep Eutectic Solvents as à-la-Carte Medium for Transition-Metal-Catalyzed Organic Processes

Solvent-Free Synthesis of α-Cyanophosphonates from β-Nitro­styrenes by Using a Deep-Eutectic Solvent Catalyst

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Product

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Solvent-Free Synthesis of α-Cyanophosphonates from β-Nitrostyrenes by Using a Deep-Eutectic Solvent Catalyst