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DOI: 10.1055/s-2007-986646
A Bulky Silylene Generated under Mild Conditions: Its Application to the Synthesis of Organosilicon Compounds
Publication History
Publication Date:
12 September 2007 (online)
Abstract
By taking advantage of the bulky silylene Tbt(Mes)Si: (1) [Tbt = 2,4,6-(Me3Si)3C6H2, Mes = 2,4,6-Me3C6H2], generated under mild conditions from disilene Tbt(Mes)Si=Si(Mes)Tbt (2) or silylene-isocyanide complexes Tbt(Mes)SiCNAr (5), the synthesis of a variety of reactive silicon compounds, such as 2H-azasilirene, 2H-phosphasilirene, vinylsiliranes, silanone (intermediate) and silacyclic compounds containing chalcogens, was achieved. In addition, some unique reactivities of silylene 1, that is, [1+2] cycloaddition reactions to benzene and naphthalene, a double addition reaction with CS2 giving a disilacyclobutanethione derivative, and insertion reactions into B-H, B-F, B-Cl, and B-B bonds, were also revealed.
1 Introduction
2 Formation of a Bulky Silylene from the Corresponding Disilene
3 Application of the Bulky Silylene to the Synthesis of Reactive Silicon Compounds
3.1 Synthesis of Silylene-Isocyanide Complexes
3.2 Synthesis of a 2H-Azasilirene and a 2H-Phosphasilirene
3.3 Synthesis of Vinylsiliranes, the Intermediates in the Reaction with Dienes
3.4 Formation of a Silanone, a Silicon-Oxygen Double-Bond Compound
3.5 Synthesis of Silacyclic Compounds Containing Chalcogens
4 New Reactivities of the Bulky Silylene
4.1 [1+2] Cycloaddition to Aromatic Compounds
4.2 Reaction with Carbon Disulfide
4.3 Insertion into B-H, B-Cl, and B-B Bonds
5 Conclusion and Outlook
Key words
divalent silicon - reactive silicon compounds - steric hindrance - silylene - disilene
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References
Present address: Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, 1-5-1 Tenjincho, Kiryu Gunma 376-8515, Japan.