Mechanism and remarkable features of photoinduced cycloaddition of phenylacetylene to mixed phosphonium-iodonium ylide

Nekipelova, T. D.; Taranova, Marina A.; Matveeva, E. D.; Podrugina, T. A.; Кузьмин, В. А.; Зефиров, Н. С.

doi:10.1134/s0012500812110092

Cited by 10 publications

(9 citation statements)

References 5 publications

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“…We have previously discussed mechanistic pathways leading to the formation of phosphonium salts 22 in the course of photodecomposition of phosphonium-iodonium ylides. [5] Schemes for the formation of phosphonium-substituted furans 21c and 21d were presented and discussed in our previous papers. [3] Clearly, the structures of phosphininofurans 17 and 18 in Scheme 4 differ from the phosphininofuran structures shown in Scheme 2.…”

Section: Resultsmentioning

confidence: 99%

“…[3] Our previous study of the reactions of triphenyl-substituted mixed ylides 1 with phenylacetylene by steady-state photolysis showed that the rate of the reaction was increased by the presence of catalytic amounts of acid. [5] Hence, it is reasonable to assume that the reason for the anomalous behaviour of furyl-substituted ylides 3a is the presence of trace amounts of acidic impurities, which can have a catalytic effect. This is reasonable, because mixed ylides 3a were all obtained as the tetrafluoroborates from the reaction mixtures by the addition of HBF 4 .…”

Section: Resultsmentioning

confidence: 99%

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Furyl‐Substituted Mixed Phosphonium–Iodonium Ylides in the Synthesis of Annelated P‐Containing Heterocyclic Compounds

et al. 2015

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Photochemical reactions between stabilized furyl‐substituted phosphonium–iodonium ylides and terminal acetylenes led to the formation of new P‐containing heterocyclic compounds. For the heterocyclization of 2‐furyl‐substituted ylides, we observed an unprecedented electrophilic ipso attack onto the α position of the furan ring in a carbocationic intermediate, leading – via a spiro intermediate – to the rearranged product with a 2,3‐shift in the furan ring.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Furyl‐Substituted Mixed Phosphonium–Iodonium Ylides in the Synthesis of Annelated P‐Containing Heterocyclic Compounds

et al. 2015

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“…The reaction is characterized by remarkable peculiarities . The formation of heterocycles 3 and 4 occurs only in DCM at [ 1 ] ≥ 0.01 mol/L.…”

Section: Introductionmentioning

confidence: 99%

“…Acetonitrile is not suitable solvent for the reaction between ylides and acetylenes, because the ylides undergo photoinduced reaction with ACN to give 2,3,5‐substituted oxazoles . The reaction with acetylenes occurs with an induction time (4‐30 min) depending on the light intensity and the purity of the ylide and DCM and then develops during several minutes . (Figure S1) It has been shown that addition of an acid decreases the induction time …”

Section: Introductionmentioning

confidence: 99%

Dichloromethane as solvent and reagent: a case study of photoinduced reactions in mixed phosphonium‐iodonium ylide

Левина

Klimovich

Vinogradov

et al. 2018

J of Physical Organic Chem

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Several years ago the photoinduced reaction of mixed phosphonium-iodonium ylides (1) with acetylenes (2) to give λ 5 -phosphinolines (3) and substituted furans (4) was described. This reaction is one-pot, metal-free synthesis of heterocycles 3 and 4 with the yields of 40% to 80%. The reaction proceeds only in dichloromethane (DCM) at the high ylide concentrations (>0.01 mol/L). The product analysis by 31 P NMR, electrospray ionization mass spectrometry, UVvis spectrophotometry, and the dynamic light scattering study of the self-aggregation of the ylide in DCM showed a dual role of the solvent in the photoinduced reactions of mixed phosphonium-iodonium ylide: (i) at the low ylide concentrations (<0.01 mol/L), the conjugated photoinitiation of the chain reaction in DCM results in the formation of chlorine-containing products and (ii) at the high ylide concentrations (>0.01 mol/L), the photolysis mechanism is determined by self-organization of the ylide molecules to give large stable aggregates in DCM, in which the target heterocycles are synthesized. Two important issues follow from the study. First, the annulation reaction between mixed phosphonium-iodonium ylide and acetylenes occurs only when the reactive intermediates are in close proximity to one other, and, second, DCM is not inert reagent in reactions occurring with participation of radicals and in one form or another can participate in photoinduced radical reactions of various solutes.KEYWORDS annulation with acetylenes, dichloromethane, phosphonium-iodonium ylides, radical reactions, selfassembly This article is dedicated with respect and affection to the memory of the late Prof. Nikolay S. Zefirov.

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“…1 These compounds have attracted considerable attention in the last decade because of their high potential in the synthesis of different important and novel heterocycles. 2 The interaction between mixed phosphonium-iodonium ylides and acetylenes allows for the synthesis of substituted phosphorus-containing heterocycles such as l 5 -phosphinolines (3) and substituted furans (4) in a simple, one-pot, metal-free reaction at room temperature. Scheme 1 is given for a particular case of mixed benzoyl ylide 1 used in this study, in the following schemes counterion BF 4 À is omitted for simplicity, because no products containing B or F were identied.…”

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CIDNP as a tool to unveil the reaction mechanism: interaction of mixed phosphonium–iodonium ylide withp-methoxyphenylacetylene

et al. 2019

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Mechanism and remarkable features of photoinduced cycloaddition of phenylacetylene to mixed phosphonium-iodonium ylide

Cited by 10 publications

References 5 publications

Furyl‐Substituted Mixed Phosphonium–Iodonium Ylides in the Synthesis of Annelated P‐Containing Heterocyclic Compounds

Furyl‐Substituted Mixed Phosphonium–Iodonium Ylides in the Synthesis of Annelated P‐Containing Heterocyclic Compounds

Dichloromethane as solvent and reagent: a case study of photoinduced reactions in mixed phosphonium‐iodonium ylide

CIDNP as a tool to unveil the reaction mechanism: interaction of mixed phosphonium–iodonium ylide withp-methoxyphenylacetylene

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