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

2 Scopus citations

Abstract

Deprotonation of 1-hydroxyalkyltris(trimethylsilyl)silanes, (Me3Si)3,Si- C(OH)R1R2 (1) with methyl lithium in ether at low temperature leads to transient silenes, (Me3Si)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-isopropyl1-,1,2,2-tetrakis- (trimethylsily1)disilane 3, (E)-3,4-di-tbutyl- 1,1,2,2-tetrakis(trirnethylsilyl)- 1,2-disilacyclobutane 4 and Q-1,2,3,8α-tetrahydro-l-mesityl-5,7,8α-~ethyl-2,2,3,3-tetr~s(trimethylsilyl)- 2,3-disilanaphthalene 5, resp. Deprotonation of la-1 c with excess organolithium reagents leads to trisilanes 6, the addition products of the nucleophilic organolithium compounds across the Si=C bond of the intermediate silenes 2a-2c. Compounds 2b and 2c can also be trapped with 2,3-dimethyl-l,3-butadienet o give the silacyclohex-3-enes 9a and 9b. The interaction of la-lc with methyllithium or sodium hydride in THF causes a 1,3-Si-0 trimethylsilyl migration resulting in formation of trimethylsiloxybis(trimethylsilyl)silylalkanes (Me3Si)2,SiH-C(OSiMe3)R1R2 1Oa-1Oc. Deprotonation of l c with methylmagnesiumbromide in THF gives (E)-2,4-dimesityl-l, 1,3,3-tetrakis(trimethylsilyl)-l,3-disilacyclobutane 12.

Original languageEnglish
Title of host publicationOrganosilicon Chemistry II
Subtitle of host publicationFrom Molecules to Materials
PublisherWiley-Blackwell
Pages389-398
Number of pages10
ISBN (Electronic)9783527619894
ISBN (Print)9783527292547
DOIs
StatePublished - Apr 25 2008

Keywords

  • Deprotonation
  • Elimination
  • Isolated
  • Magnesium bromide
  • Sodium hydride

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