Palladium-catalyzed rearrangement of silanes containing oxygen or halogen α to silicon

Gevorgyan, Vladimir; Borisova, L.; Lukevies, Edmunds

doi:10.1016/0022-328x(92)85060-a

Cited by 10 publications

(3 citation statements)

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“…The rearrangement of 2-(dimethylsilyl)tetrahydrofuran to the corresponding oxasilacyclohexane product has been previously reported by Lukevics and co-workers. 15,16 In their study, the authors report that the rearrangement reaction is catalyzed by Pd/Al 2 O 3 (eq 6), and a labeling experiment confirmed that the Si−H/D bond was being cleaved in order for the rearrangement to occur.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Syntheses, Characterization, and Reactivity of Diruthenium Hydrido Complexes

et al. 2016

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International audienceThe reaction of [cis-₍η5-C5H3)2(CMe2)2_Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2(MeCN)2][OTf]2, 1, with H2 yields a μ-dihydrido complex, [cis-₍η5-C5H3)2(CMe2)2_Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2(μ-H)2][OTf]2, 2, in 79% yield. The reaction of 2 with Et3SiH affords a mono-μ-hydrido complex, cis-₍η5-C5H3)2(CMe2)2_Ru2(κ2-4,4′-di-tert-butyl-2,2′-bipyridine)2(μ-H)][OTf], 3. The reaction of either 2 or 3 (1-2 mol %) with C6H6 and Et3SiH results in the catalytic cleavage of the C-H bond in benzene along with the cleavage of the Si-Et bond to form PhEt2SiH (23-27% conversion) and C2H6. The reaction of 2 or 3 (1 mol %) with THF and Et3SiH results in the cleavage of the C-H bond in THF followed by the insertion of the SiEt2 group into the C-O bond, forming 2,2-diethyl-1-oxa-2-silacyclohexane (14% conversion) as one of the products. © 2016 American Chemical Society

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Section: ■ Results and Discussionmentioning

confidence: 99%

Syntheses, Characterization, and Reactivity of Diruthenium Hydrido Complexes

et al. 2016

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“…Migration of a silyl group from carbon to heteroatom (O, N, S) is a key step in numerous intramolecular rearrangements of carbofunctional organosilicon compounds which have been long investigated both experimentally and theoretically. [1][2][3][4][5][6][7][8][9][10][11][12] The rearrangements proceed under anionotropic or cationotropic, 8 as well as catalytic 9,10 or thermal conditions. 1,2 Among these, of special mechanistic and synthetic interest, is the sila-Pummerer rearrangement.…”

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confidence: 99%

“…Migration of a silyl group from carbon to heteroatom (O, N, S) is a key step in numerous intramolecular rearrangements of carbofunctional organosilicon compounds which have been long investigated both experimentally and theoretically. − The rearrangements proceed under anionotropic or cationotropic, as well as catalytic 9,10 or thermal conditions. , Among these, of special mechanistic and synthetic interest, is the sila-Pummerer rearrangement. It was discovered by Brook in 1968 13 as thermal conversion of linear α-silyl sulfoxides into siloxymethyl sulfides and has been widely used in organic synthesis for the preparation of carbonyl compounds, 14 vinyl sulfides, − etc. ,− However, its mechanism is not as yet fully understood although various assumptions have been made on the basis of the experiments .…”

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confidence: 99%