The Synthesis of Transient Silenes using the Principle of the Peterson Reaction

Clemens Krempner, Helmut Reinke, Hartmut Oehme

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

Abstract

Deprotonation of 1-hydroxyalkyltris(trimethylsilyl)silanes, (Me3Si)3Si-C(OH)R1R2 (1) with methyl lithium in ether at low temperature leads to transient silenes, (MeSi2)2Si=CR1R2 (2a: R1 = R2 = Me; 2b: R1 = H, R2 = tBu; 2c: R1 = H; R2 = Mes), which dimerize in absence of trapping agents to give 1-isopropenyl-2-isopropyl-1,1,2,2-tetrakis-(trimethylsilyl)disilane 3, (E)-3,4-di-/butyl-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclo-butane 4 and (E)-1,2,3,8α-tetrahydro-l-mesityl-5,7,8α-trmiethyl-2,2,3,3-tetrakis(trimethyl-silyl)-2,3-disilanaphthalene 5, resp. Deprotonation of 1a-1c with excess organolithium reagents leads to trisilanes 6, the addition products of the nucleophilic organolithium compounds across the SiC bond of the intermediate silenes 2a-2c. Compounds 2b and 2c can also be trapped with 2,3-dimethyl-1,3-butadiene to give the silacyclohex-3-enes 9a and 9b. The interaction of 1a-1c with methyllithium or sodium hydride in THF causes a 1,3-Si-O trimethylsilyl migration resulting in formation of trimethylsiloxybis(trimethylsilyl)silyl-alkanes (Me3Si)2SiH-C(OSiMe3)R1R2 10a-10c. Deprotonation of 1c with methylmagnesium-bromide in THF gives (E)-2,4-dimesityl-1,1,3,3-tetrakis(trimethylsilyl)-1,3-disilacyclobutane 12

Original languageEnglish
Title of host publicationOrganosilicon Chemistry Set
Subtitle of host publicationFrom Molecules to Materials
PublisherWiley
Pages389-398
Number of pages10
ISBN (Electronic)9783527620777
ISBN (Print)9783527323470
DOIs
StatePublished - Jun 10 2008

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