Photochemistry of alkyl halides. 10. Vinyl halides and vinylidene dihalides

Kropp, Paul J.; McNeely, Steven A.; Davis, Robert D.

doi:10.1021/ja00361a028

Cited by 64 publications

(34 citation statements)

References 1 publication

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“…2a,b). Inspired by Kropp's seminal work [25][26][27][28] on the heterolytical cleavage of alkyl C-I bond to form carbocations under ultraviolet irradiation in highly polar solvents, we hypothesized that by harmonizing the rate of C-I bond cleavage (related to the light intensity) and the nucleophilicity of the terminal alkyne, the coupling between alkynes and alkyl iodides can be accomplished directly via radical or carbocation intermedates, in the absence of any transiton metals (Fig. 2c).…”

Section: Resultsmentioning

confidence: 99%

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Liu

2015

Nat Commun

135

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Methods to assemble alkynes are essential for synthesizing fine chemicals, pharmaceuticals and polymeric photo-/electronic materials. Using light as a clean energy form and water as a green solvent has the potential to make synthetic chemistry more environmentally friendly. Here we present a transition-metal-free coupling protocol between aryl alkyne and alkyl iodide enabled by photoenergy in water. Under ultraviolet irradiation and in basic aqueous media, aryl alkynes efficiently couple with a wide range of alkyl iodides including primary, secondary and tertiary ones under mild conditions. A tentative mechanism for the coupling is also proposed.

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Section: Resultsmentioning

confidence: 99%

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Liu

2015

Nat Commun

135

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“…In particular, the signals for H-2 and H-4 each appear as a doublet of doublets (J = ca. [7][8][9][10][11][12][13][14]; the larger couplings are consistent with a trans orientation with H-1 and H-5 respectively. The chemical shifts and coupling constants for 9a are similar to those reported for the (1-methoxycarbonyl-5-phenylpentadienyl)Fe(CO)3 + cation 9b.…”

Section: Resultsmentioning

confidence: 99%

“…6,6-Dimethyl-1-iodocyclohexene was prepared from 2,2-dimethylcyclohexanone according to the literature procedure. 9 accessed by following the link in the citation at the bottom of the page. Chemistry, Vol.…”

Section: Experimental General Methodsmentioning

confidence: 99%

Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins

et al. 2011

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A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)3 + cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)3. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)3 along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl2, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.

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“…The 1-iodocyclohexene 3 was prepared from ketone 1 by using some modifications of the general method of Pross and Sternhell [6] Irradiation of 1-iodocyclohexene (3) in methanol (λ = 254 nm, Figure 1) afforded a mixture of the dimethyl ketal 6, enol ether 5 and cycloalkene 4 [7] (Scheme 2). Product 6 arises from an acidcatalyzed addition of methanol to the nucleophilic trapping product 5.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Photochemistry of 1-Iodocyclohexene:Influence of Ultrasound on Ionic vs. Radical Behaviour

Blaškovicová

Gáplovský²,

Blaško³

2007

Molecules

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Simultaneous application of UV light and ultrasonic irradiation to a reaction mixture containing 1-iodocyclohexene is reported. The irradiation of 1-iodocyclohexene in methanol was carried out with or without addition of zinc. The effect of ultrasound or mechanical stirring on this solid-liquid system was also compared. The irradiation of 1-iodocyclohexene in methanol in the presence of zinc increases the yield of the nucleophilic trapping product, compared with the yield after irradiation in the absence of zinc. The photodegradation of 1-iodocyclohexene was slightly accelerated after addition of zinc. A rapid formation of radical product was accompanied by substantial decrease of 1-iodocyclohexene after application of ultrasound and irradiation without the zinc. The ultrasound significantly affects the photobehaviour of this reaction, predominantly its radical route. The joint application of ultrasound and zinc contributes positively to the production of radical and ionic products. The sonochemical stirring is more effective than mechanical stirring.

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Photochemistry of alkyl halides. 10. Vinyl halides and vinylidene dihalides

Cited by 64 publications

References 1 publication

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins

Synthesis and Photochemistry of 1-Iodocyclohexene:Influence of Ultrasound on Ionic vs. Radical Behaviour

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