Substituent Effects on the Reactivity of the Silicon−Carbon Double Bond

Morkin, Tracy L.; Leigh, William J.

doi:10.1021/ar960252y

Cited by 100 publications

(57 citation statements)

References 78 publications

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“…It is well known that disilane molecules having a siliconsilicon σ bond show unique properties in the photochemical [1][2][3][4] and thermal reactions 5 and in the transition metal catalyzed reactions [6][7][8][9][10][11][12][13][14] since the first reports on the unusual electronic spectra of aryldisilanes by Sakurai et al, 15 Gilman et al 16 and Hague et al 17 in 1964. In the context of our interest on the synthesis of silicon containing heterocyclic compounds by the photoreactions of ortho-substituted arylalkynyldisilanes [18][19][20][21][22][23][24][25][26][27][28][29] and aryldisilanes, 30,31 we have very recently reported on the photoreaction of (2-pentamethyldisilanyloxy)phenylpentamethyldisilane 32 in the presence of methanol or acetone affording a novel intramolecular photoproduct via silene intermediate.…”

Section: Methodsmentioning

confidence: 99%

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Park¹,

Gong²

2010

Bulletin of the Korean Chemical Society

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Section: Methodsmentioning

confidence: 99%

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Park¹,

Gong²

2010

Bulletin of the Korean Chemical Society

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“…14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O…”

Section: 13mentioning

confidence: 99%

“…14, 15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O [23][24][25][26] , and C=C 27-31 bonds resulted in the formation of the addition products.…”

Section: 13mentioning

confidence: 99%

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

Park¹,

Kim²

2011

Bulletin of the Korean Chemical Society

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It is well known that the photoreactions of aryldisilanes show four reaction patterns 1 since the first report on the photolysis of phenylpentamethyldisilane and (p-tolyl)pentamethyldisilane by Ishikawa et al.2 in 1975 : (path a) formation of a silene compound via elimination of a trimethylsilane 3 , (path b) formation of a silene compound arising from 1,3-shift of trimethylsilyl radical, which is formed via homolytic cleavage of silicon-silicon bond [4][5][6][7][8][9] , (path c) formation of a trimethylsilyl compound via elimination of a silylene 10,11 , (path d) formation of a direct solvolysis compound via elimination of a trimethylalkoxysilane or pentamethylalkoxydisilane. 12,13Silenes having the C=Si moiety are regarded as highly interesting intermediates. Consequently the synthesis and reactions of silenes as useful intermediates have been extensively investigated.14,15 The intermolecular reactions between highly unstable silenes and the compounds containing functional groups such as OH [16][17][18][19][20][21][22] , C=O 23-26, and C=C 27-31 bonds resulted in the formation of the addition products.In connections with the photolysis of aryldisilanes, we recently disclosed the intramolecular reactions between the silene intermediates resulted from the photoreactions of ortho-substituted aryldisilanes and ortho-substituents to give the novel silicon-containing heterocyclic compounds such as the photoinduced intramolecular reactions of (2-substitutedphenyl)pentamethyldisilanes 32 , (2-alkoxymethylphenyl)pentamethyldisilanes 33 , 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 34 and (2-hydroxyethoxyphenyl)pentamethyldisilane. 35 We have also investigated the synthesis of siliconcontaining heterocyclic compounds through the intramolecular reactions of silacyclopropene or 1-silaallene moiety with ortho-substituents in ortho-substituted-phenylethynylpentamethyldisilanes 36. As a part of our continuous studies utilizing the silenes as reaction intermediates for the synthesis of silicon-containing heterocyclic compounds, we investigated the photoreactions of (2-acetoxyphenyl)pentamethyldisilane which has the acetoxy group as ortho substituent to phenylpentamethyldisilane because it was expected that the novel photoproducts could be formed from the intramolecular reaction of ortho-substituted acetoxy group with the silene intermediate. In this note, we would like to report the detailed photochemical study of (2-acetoxyphenyl)pentamethyldisilane.The starting (2-acetoxyphenyl)pentamethyldisilane 2 was prepared from the reaction of (2-hydroxyphenyl)pentamethyldisilane 1 35 with acetyl chloride using triethylamine as base in tetrahydrofuran at room temperature (Scheme 1).In order to investigate a possibility that the C=O bond as ortho substituent in 2 reacts intramolecularly with a silene, the photolysis of 2 was performed.Irradiation of 2 in deaerated benzene with 254nm UV light afforded two photo-Fries rearrangement products 4 (18% yield) and 5 (10% yield) along with some decomposition products of unknown structu...

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“…All silenes thus formed react with various trapping agents, such as alcohols, [10][11][12][13][14][15][16][17] carbonyl compounds, [18][19][20][21] alkenes, [22][23][24][25][26][27][28][29] and alkynes 30 to give the addition products and in the absence of such trapping agents, dimerization products of silene intermediates were obtained. 31,32 The photolysis of the aromatic compounds having two pentamethyldisilanyl groups, such as 1,2-, 1,3-, 1,4-bis(pentamethyldisilanyl)-benzenes, 33 1,4-, 1,5-bis(pentamethyldisilanyl)naphthalenes 34 also affords the silene intermediates but in the case of 4,4'-bis(pentamethyldisilanyl)biphenyl, 35 the photoproducts from the silene intermediate were not obtained.…”

Section: Introductionmentioning

confidence: 99%

Photoreactions of 2-(Pentamethyldisilanyloxy)phenylpentamethyldisilane

2008

Bulletin of the Korean Chemical Society

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Photolysis of 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 1 in methanol provides five photoproducts 3, 4, 5, 6, and 7. Compounds 3 and 4 were probably formed from the methanol addition reactions of silene intermediate 2 and the formation of 5, 6, and 7 can best be explained by the nucleophilic attack of methanol to silicon atom in pentamethyldisilanyloxy or pentamethyldisilanyl group of the photoexcited state of 1. Irradiation of 1 in n-hexane gives a photoproduct 6 via silyl radical intermediate 8 and a novel intramolecular cyclization photoproduct 11 via silene 9 and silyl radical intermediate 10. Irradiation of 1 in deaerated methylene chloride in the presence of acetone affords a novel photoproduct 11 and phenol 7 but the expected photoproducts from the reaction of the silene intermediate with acetone were not obtained.

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Substituent Effects on the Reactivity of the Silicon−Carbon Double Bond

Cited by 100 publications

References 78 publications

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Photoinduced Rearrangement Reaction of 2-(Pentamethyldisilanyloxymethyl) phenylpentamethyldisilane

Photoreactions of (2-Acetoxyphenyl)pentamethyldisilane

Photoreactions of 2-(Pentamethyldisilanyloxy)phenylpentamethyldisilane

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