Radical ions in photochemistry. 4. The 1,1-diphenylethylene anion radical by photosensitization (electron transfer)

Arnold, Donald R.; Maroulis, A. J.

doi:10.1021/ja00464a044

Cited by 33 publications

(15 citation statements)

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“…The corresponding photohydration worked only if the aromatic olefins as starting material were directly excited by UV light [15,16]. The first approach towards a photocatalytic version of this type of reaction came from Arnold, Maroulis et al [17,18]. They demonstrated that electron-rich naphthalenes are able to photoinitiate methanol additions to olefins into the Markovnikov orientation and proposed an oxidative electron transfer mechanism for this process [17].…”

Section: Introductionmentioning

confidence: 99%

“…The first approach towards a photocatalytic version of this type of reaction came from Arnold, Maroulis et al [17,18]. They demonstrated that electron-rich naphthalenes are able to photoinitiate methanol additions to olefins into the Markovnikov orientation and proposed an oxidative electron transfer mechanism for this process [17]. Complementarily, electron-poor naphthalenes yielded the anti-Markovnikov-type addition of cyanide to styrene [18].…”

Section: Introductionmentioning

confidence: 99%

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Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

Weiser¹,

Hermann²,

Penner³

et al. 2015

Beilstein J. Org. Chem.

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The nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the reductive mode towards the Markovnikov-type regioselectivity, Py was applied as photocatalyst and triethylamine as electron shuttle. This approach was also used for intramolecular additions. For the oxidative mode towards the anti-Markovnikov-type regioselectivety, PDI was applied together with Ph–SH as additive. Photocatalytic additions of a variety of alcohols gave the corresponding products in good to excellent yields. The proposed photocatalytic electron transfer mechanism was supported by detection of the PDI radical anion as key intermediate and by comparison of two intramolecular reactions with different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as “green” light source.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

Weiser¹,

Hermann²,

Penner³

et al. 2015

Beilstein J. Org. Chem.

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“…Mizuno and Otsuji(61l have shown that nucleophilic heteroaromatic compounds like furans and pyrroles can add to radical cations generated from olefins by electron transfer sensitization. Thus, irradiation of l-cyanonaphthalene in acetonitrile solutions containing 1,1-diphenylethylene and a series of substituted furans gave mixtures of 1: 1 and 1:2 adducts in high yields, as illustrated by transformations producing [64][65][66]. No olefin-furan crossed additions were observed when the bis-p-methoxyphenyl-substituted olefin was employed, owing presumably to the stability tophysical studies have shown that the initial step in the mechanism for these additions involves electron transfer from the olefin rather than the heteroaromatic system to the singlet excited sensitizer.…”

Section: Alkenes As Electron Acceptors and Donorsmentioning

confidence: 99%

Synthetic Aspects of Photochemical Electron Transfer Reactions

Mariano

Stavinoha

1984

Synthetic Organic Photochemistry

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“…Useful synthetic applications, such as the radicalcation-catalyzed cycloaddition [14][15][16][17][18][19][20] or the anti-Markovnikov addition of nucleophiles to alkenvl radical cations [21][22][23][24][25], have been well documented. In analogy, the addition of electrophiles to alkenyl radical anions in a Markovnikov fashion has been intensively studied [24,26]. Perhaps the largest class of radical anion fragmentation reactions is represented by the aromatic nuleophilic substitution via the SRN1 mechanism.…”

Section: Introductionmentioning

confidence: 99%