A Facile Synthesis of α -Iodo- β -nitroalkenes from Alkynes Using I2/NO3− or KI/NO3−

Yusubov, M. S.; Perederina, I. A.; Филимонов, В. Д.; Park, Tae-Ho; Chi, Ki‐Whan

doi:10.1080/00032719808006480

Cited by 20 publications

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“…In an earlier report, we demonstrated, that SO 3 in the presence of sodium or ammonium nitrate effected an oxidative heterocyclization of phenylacetylene to 3-benzoyl-5-phenylisoxazole [4]. The later result is in contrast to the behavior of the NaNO 3 /I 2 (or KI) systems which only leads to iodonitration of the alkynes [5].…”

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confidence: 44%

“…Previously, we have showed that nitroyl halides X-NO 2 (X=F, Cl, Br, I) are intermediates in the reaction of NaNO 3 with sodium or potassium halides in acetic acid [12]. Nitroyl fluoride and chloride only possess nitrating activity, where as the bromide and the iodide are halogenation reagents for alkynes, arenes and heteroaromatics [5,12]. Taking these results into account, it seems likely that the same intermediates are veritable reagents in the reaction of alkynes with the NaNO 3 /NaF(KCl)/AcOH system, and accordingly in the case of NaNO 3 /NaHSO 4 (or SO 3 )/AcOH.…”

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Simple synthesis of 3-acyl-5-alkyl(aryl)isoxazoles from terminal alkynes and nitrates of alkaline metals or ammonium

et al. 2005

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A simple and general synthesis of 3-acyl-5-alkyl(aryl)isoxazoles by reaction of terminal alkynes with nitrates in acetic acid in the presence of SO 3 or alkaline salts is described. c Central European Science Journals. All rights reserved. Keywords: Alkynes, isoxazoles, nitrates, sulfur trioxideIn continuation of our ongoing program to develop synthetically useful reactions of alkynes with SO 3 , we have found that SO 3 can be an effective reagent or mediator for novel transformations of the triple bond. Phenylacetylene on treatment with SO 3 in H 2 SO 4 , yields δ-sultone -4,6-diphenyl-[1,2]oxathiine-2,2-dioxide [1]. The reaction of internal alkynes with the SO 3 /DMSO/CCl 4 system leads to 1-chloro-2-methylthioethenes [2]. In contrast, the SO 3 -dioxane complex easily oxidizes triple bonds of internal alkynes or dialkynes to 1,2-diketones or bis(1,2-diketones) [3]. In an earlier report, we demonstrated, that SO 3 in the presence of sodium or ammonium nitrate effected an oxidative heterocyclization of phenylacetylene to 3-benzoyl-5-phenylisoxazole [4]. The later result is in contrast to the behavior of the NaNO 3 /I 2 (or KI) systems which only leads to iodonitration * E-mail: filimonov@tpu.ru Isoxazoles play interesting roles in medicinal and agricultural chemistry and serve as important synthetic building blocks (e.g., see [6,7] and refs therein).The two accepted general approaches for the formation of izoxaloles are: condensation of 1,3-dicarbonyl compounds with hydroxylamine and 1,3-bipolar cycloaddition of nitrile oxides to alkynes [6].A few methods are known for the synthesis of isoxazoles from terminal alkynes. The reaction of acetylene gas with fuming nitric acid gives rise to a mixture of isoxazoles bearing oxygen-containing substituents in the 3 position [8]. However, Gasparrini et al. found that terminal alkynes (R=Ph, n−Pr, n−Bu, BzOC 2 H 4 ) react with nitric acid under biphasic conditions (nitromethane/water) and in the presence of a catalytic amount of tetrabutylammonium tetrachloroaurate to give 3,5-disubstituted isoxazoles in 30-55 % yield [6]. Recently, it has been shown that the reaction of phenylacetylene with acetone or acetophenone in the presence of an equimolar amount of ammonium cerium nitrate resulted in the formation of 3-acetyl-or 3-benzoylisoxazoles with a 57-85 % analytical yield (GLC data) [7]. Another approach to this class of compounds is to react phenylacetylenes and α-nitrocarbonyl compounds [9,10] in solid phase [11]. In almost all above mentioned cases , preparative yields of the isoxazoles are very modest and the employed reagents are expensive and unsafe. Therefore, there is still a demand for new mild synthetic methods for the preparation of isoxazoles from alkynes in the presence of inexpensive and bench top reagents.Since nitrates of alkali metals are cheap, environmentally friendly, and safe to handle, we decided to explore the possibility of using the SO 3 /NO − 3 system in the reaction with alkynes for isoxazole syntheses starting from alkynes.We have shown...

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Simple synthesis of 3-acyl-5-alkyl(aryl)isoxazoles from terminal alkynes and nitrates of alkaline metals or ammonium

et al. 2005

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“…A plausible reaction mechanism is proposed on the basis of the above control experiments and previous reports (Scheme ). ,, Initially, the aromatic terminal alkynes 1 is transformed into adduct M-1 in the presence of Fe(NO 3 ) 3 and KI. Then M-1 reacts with H 2 O under iron-mediated conditions, and intermediate M-2 was formed.…”

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confidence: 99%

“…So M-1 and M-2 might be the intermediates for the formation of target product 4a. Furthermore, 1a could be transformed to M-1 in the presence of KI and NaNO 3 , 16 and then M-1 could be transformed into product 4a successfully without the addition of KI under Fe(NO 3 ) 3 -mediated conditions (Scheme 4B). The result also implied that M-1 should be the intermediate and that KI was not necessary in the subsequent formation of isoxazole 4a after intermediate M-1 was generated.…”

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confidence: 99%

Iron-Mediated Synthesis of Isoxazoles from Alkynes: Using Iron(III) Nitrate as a Nitration and Cyclization Reagent

Lai

Liu

et al. 2017

J. Org. Chem.

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A simple and direct method for the iron(III) nitrate-mediated synthesis of isoxazoles from alkynes has been developed; both self-coupling and cross-coupling products could be successfully prepared from alkynes. Meanwhile, for the cross-coupling and cyclizing of two different alkynes examined, the iron-mediated system shows a good chemoselectivity for the synthesis of corresponding isoxazoles. In our method, cheap and eco-friendly iron(III) nitrate is used as the nitration and cyclization reagent, and KI is used as the additive; they both play a positive role in this transformation. Furthermore, a different mechanism for the formation of isoxazoles from alkynes has been proposed.

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“…Normally, there are two main ways to realize such a transformation. One is the intermolecular radical trapping reaction, which remained undeveloped until the past decade. , In this way, 2-nitrovinyl radicals can be captured by iodine or TEMPO, forming polysubstituted nitroolefins (Scheme a). The other is the intramolecular radical trapping reaction in which 2-nitrovinyl radicals first undergo a radical cyclization when an unsaturated bond is incorporated at an appropriate position .…”

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Nitration and Cyclization of Arene-Alkynes: An Access to 9-Nitrophenathrenes

2018

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A nitration and cyclization of arene-alkynes has been developed, affording 9-nitrophenathrenes efficiently. This reaction probably proceeds via addition of the nitrogen dioxide to the alkyne moiety, intramolecular radical addition of vinyl radical to one aryl ring, oxidation of radical intermediate into carbocation species, and elimination of a proton. In this transformation, Fe(NO) was used as both nitro source and oxidant.

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A Facile Synthesis of α -Iodo- β -nitroalkenes from Alkynes Using I₂/NO₃⁻ or KI/NO₃⁻

Cited by 20 publications

References 3 publications

Simple synthesis of 3-acyl-5-alkyl(aryl)isoxazoles from terminal alkynes and nitrates of alkaline metals or ammonium

Simple synthesis of 3-acyl-5-alkyl(aryl)isoxazoles from terminal alkynes and nitrates of alkaline metals or ammonium

Iron-Mediated Synthesis of Isoxazoles from Alkynes: Using Iron(III) Nitrate as a Nitration and Cyclization Reagent

Nitration and Cyclization of Arene-Alkynes: An Access to 9-Nitrophenathrenes

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