Heterocycles from Phosphonium−Iodonium Ylides. Photochemical Synthesis of λ<sup>5</sup>-Phosphinolines

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

doi:10.1021/jo901984q

Cited by 47 publications

(26 citation statements)

References 31 publications

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“…Iodonium ylides can be converted to singlet carbenes under irradiation using a mercury (Hg) lamp, and the groups of Hadjiarapoglou, Matveeva, and Spyroudis have reported examples of cyclopropanation and related cycloaddition events. These reactions thus proceed via free carbenes, which are formed upon cleavage of the ylide C−IPh bond, but the heat generated by the lamp is often an unavoidable source of technical complications and chemical selectivity issues.…”

Section: Introductionmentioning

confidence: 99%

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

et al. 2019

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A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures of alkenes and β‐dicarbonyl‐derived iodonium ylides are irradiated with light from blue LEDs. This metal‐free synthesis gives cyclopropanes in yields up to 96 %, is operative with cyclic and acyclic ylides, and proceeds with a variety of electronically‐diverse alkenes. Computational analysis explains the high selectivity observed, which derives from exclusive HOMO to LUMO excitation, instead of free carbene generation. The procedure is operationally simple, uses no photocatalyst, and provides access in one step to important building blocks for complex molecule synthesis.

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Section: Introductionmentioning

confidence: 99%

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

et al. 2019

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“…Several years ago the photoinduced reaction of various mixed phosphonium‐iodonium ylides ( 1 ) with different acetylenes ( 2 ) to give λ 5 ‐phosphinolines ( 3 ) and substituted furans ( 4 ) was described (Scheme ; in all schemes, counterion BF 4 − is omitted) . This reaction is one‐pot, metal‐free synthesis of heterocycles 3 and 4 with the yields of 40% to 80%.…”

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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“…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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Heterocycles from Phosphonium−Iodonium Ylides. Photochemical Synthesis of λ⁵-Phosphinolines

Cited by 47 publications

References 31 publications

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

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

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

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Heterocycles from Phosphonium−Iodonium Ylides. Photochemical Synthesis of λ5-Phosphinolines

Cited by 47 publications

References 31 publications

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

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

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

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Heterocycles from Phosphonium−Iodonium Ylides. Photochemical Synthesis of λ⁵-Phosphinolines