Oxidative Coupling of Lithium Silenolates:  First Synthesis of Bis(acyl)-Substituted Polysilanes

Ohshita, Joji; Masaoka, Shin; Ishikawa, Mitsuo

doi:10.1021/om960048e

Cited by 30 publications

(10 citation statements)

References 6 publications

(3 reference statements)

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“…Both types of lithium silenolates react readily with electrophiles, such as water, alkyl halides, and chlorosilanes, to produce coupling products. We have also reported that oxidative coupling reactions of lithium silenolates with palladium dichloride afford the first examples of bis(acyl)-substituted polysilanes in high yields …”

Section: Introductionmentioning

confidence: 95%

Silicon−Carbon Unsaturated Compounds. 60. Reactions of Lithium Silenolates with Dienes

et al. 1997

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The chemical properties of lithium silenolates toward dienes were studied. The reaction of lithium 2-tert-butyl-1,1-bis(trimethylsilyl)silen-2-olate (1a) with butadiene at −40 °C, followed by hydrolysis, afforded 2-tert-butyl-1,1-bis(trimethylsilyl)silacyclohex-4-en-2-ol, derived from [2 + 4] cycloaddition of 1a with butadiene, in 94% yield. Similar treatment of lithium 2-adamantyl-1,1-bis(trimethylsilyl)silen-2-olate (1b) gave the respective adduct in 87% yield. The reactions of lithium silenolates 1a,b with 2,3-dimethylbutadiene, isoprene, and 1,3-pentadiene proceeded in a fashion similar to those with butadiene to give the [2 + 4] cycloadducts in high yields. The reactions of 1a,b with 2,3-dimethylbutadiene and butadiene at room temperature gave the products originated from 1,1-bis(trimethylsilyl)silacyclohexa-1,4-diene intermediates. The crystal structure of 10-adamantyl-2,3,6,7-tetramethyl-9-(trimethylsilyl)-9-silabicyclo[4.4.0]deca-2,6-diene (6b), which was obtained from the reaction of 1b with 2,3-dimethylbutadiene at room temperature, was determined by a single-crystal X-ray diffraction study.

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Section: Introductionmentioning

confidence: 95%

Silicon−Carbon Unsaturated Compounds. 60. Reactions of Lithium Silenolates with Dienes

et al. 1997

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“…These findings are wholly consistent with those of their NMR spectrometry, which shows that the anionic charge is sufficiently delocalized over the Si−C−O unit in the aryl-substituted silenolates, while the anionic charge in the alkyl-substituted silenolates localizes moderately on the central silicon atoms. Quite recently, we have also demonstrated that treatment of lithium silenolates with palladium dichloride gives the oxidative coupling products bis(acyl)-substituted polysilanes …”

Section: Introductionmentioning

confidence: 97%

Reactions of Lithium Silenolates with Carbonyl Compounds

et al. 1997

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The chemical behavior of lithium silenolates, (Me3Si)2SiC(OLi)R (1a, R = Mes; 1b, R = t-Bu), toward carbonyl compounds was studied. Treatment of lithium silenolates 1a and 1b with benzaldehyde and then with chlorotriethylsilane afforded products derived from the reactions of the lithium silenolates with 2 equiv of benzaldehyde, followed by coupling of the resulting anions with chlorotriethylsilane, in good yields. Treatment of 1a and 1b with mesityl aldehyde under the same conditions proceeded similarly to give the respective adducts in high yields, while the reaction of 1a with acetophenone gave the adduct only in low yield. Similar reactions of 1a and 1b with mesityl methyl ketone, however, afforded no adducts but produced lithium 1-mesitylethenolate and the respective acylbis(trimethylsilyl)silanes.

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“…Lithium silenolates are silicon analogues of lithium enolates and react readily with several electrophiles, such as alkyl halides, carbonyl compounds, and dienes . We have also demonstrated that oxidative coupling of lithium silenolates with palladium dichloride leads to the formation of bis(acyl)polysilanes as the first example of polysilanes with two Si-acyl bonds on the adjacent silicon atoms . In this paper, we report the first synthesis of compounds having a silicon atom with di- and tetraacyl substitution, by the reactions of lithium silenolates with acyl halides.…”

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confidence: 95%

Reactions of Lithium Silenolates with Acyl Halides. First Synthesis of Di- and Tetraacylsilanes

1999

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Oxidative Coupling of Lithium Silenolates: First Synthesis of Bis(acyl)-Substituted Polysilanes

Cited by 30 publications

References 6 publications

Silicon−Carbon Unsaturated Compounds. 60. Reactions of Lithium Silenolates with Dienes

Silicon−Carbon Unsaturated Compounds. 60. Reactions of Lithium Silenolates with Dienes

Reactions of Lithium Silenolates with Carbonyl Compounds

Reactions of Lithium Silenolates with Acyl Halides. First Synthesis of Di- and Tetraacylsilanes

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