Initiated pseudo-[3+2] cycloaddition of mixed phosphonium-iodonium ylides to acetonitrile

Matveeva, E. D.; Podrugina, T. A.; Pavlova, Anna S.; Миронов, А. В.; Зефиров, Н. С.

doi:10.1007/s11172-008-0313-3

Cited by 18 publications

(13 citation statements)

References 8 publications

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“…However, when we heated 4 and DMAD in acetonitrile as solvent at 80°C we obtained 9a in 30 % yield (Scheme 3). [8] The product can be explained as arising from 4 by cycloaddition with the CϵN bond. The amazing feature of this process is that no reaction between ylide 4 and acetonitrile was observed in the absence of DMAD.…”

Section: Resultsmentioning

confidence: 99%

Novel Photochemical Reactions of Phosphonium‐Iodonium Ylides: Synthesis of Phosphonium‐Substituted Oxazoles

et al. 2009

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Section: Resultsmentioning

confidence: 99%

Novel Photochemical Reactions of Phosphonium‐Iodonium Ylides: Synthesis of Phosphonium‐Substituted Oxazoles

et al. 2009

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“…Ylide 1 and reaction products 2 , 4 , and 5 were synthesized according to the procedures described elsewhere . Acetonitrile (BIOSOLVE (B.V., Valkenswaard, Netherlands), 99.95%) was dried according to the standard procedure .…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we have described two novel photochemical reactions of ylides of type 1 in the presence of compounds with triple bond, which afford products of pseudocycloaddition. The reactions proceed in different modes depending on the character of the triple bond . Nitriles R 1 CN give corresponding oxazoles ( 2 ), with PhI ( 3 ) being a leaving group (Scheme ), while the reaction between phosphonium–iodonium ylides of type 1 and acetylenes gives λ 5 ‐phosphinolines …”

Section: Introductionmentioning

confidence: 99%

On the mechanism of photoinduced addition of acetonitrile to phosphonium–iodonium ylides

Nekipelova

Кузьмин

Matveeva

et al. 2012

J of Physical Organic Chem

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Recently, a novel photochemical reaction of pseudocycloaddition of nitriles to mixed phosphonium-iodonium ylides 1 was found. Nitriles R 1 CN give corresponding oxazoles (2) with a high yield, with PhI (3) being a leaving group. The mechanism of the photoinduced cycloaddition of acetonitrile to mixed phosphonium-iodonium ylide 1 was studied by steady-state and time-resolved methods with resolution from 10 ns to 20 ms. The formation of photolysis products, substituted oxazole 2, and phosphonium salt 4, occurs in parallel reactions. The primary photochemical processes for the formation of 2 and 4 are the heterolytic and homolytic C-I + Ph bond cleavage in the excited singlet state of 1, respectively. Three transient species with lifetimes on microsecond and millisecond time scales were observed. The mechanism of the formation of major and minor products of the photolysis was suggested. Addition of water to the reaction mixture in acetonitrile changes the ratio of the products in favor of the phosphonium salt formation. The effect of water was accounted for by the acid catalysis of the homolytic C-I + Ph bond cleavage and the acceleration of the salt formation.

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“…Zefirov, Matveeva, and co-workers have demonstrated the utility of mixed phosphoniumiodonium ylides as reagents for the synthesis of various heterocyclic systems such as: substituted oxazoles, 92,111 phosphonium-substituted furans, 46 substituted phosphinolines, 46,91,93,94 and annelated phosphorus-containing heterocycles. [112][113][114][115] All these cycloadditions proceed under photochemical conditions.…”

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confidence: 99%

Iodonium ylides in organic synthesis

Yusubov

Yoshimura

Zhdankin³

2016

Arkivoc

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This review summarizes the chemistry of iodonium ylides with emphasis on their synthetic applications. The preparation, structure and chemistry of iodonium ylides of different structural types are overviewed. Iodonium ylides have found synthetic application as efficient carbene precursors, especially useful as reagents for cyclopropanation of alkenes and preparation of heterocyclic compounds. Recently iodonium ylides have been utilized as efficient reagents in the thiotrifluoromethylation and nucleophilic fluorination reactions.

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Initiated pseudo-[3+2] cycloaddition of mixed phosphonium-iodonium ylides to acetonitrile

Cited by 18 publications

References 8 publications

Novel Photochemical Reactions of Phosphonium‐Iodonium Ylides: Synthesis of Phosphonium‐Substituted Oxazoles

Novel Photochemical Reactions of Phosphonium‐Iodonium Ylides: Synthesis of Phosphonium‐Substituted Oxazoles

On the mechanism of photoinduced addition of acetonitrile to phosphonium–iodonium ylides

Iodonium ylides in organic synthesis

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