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Volumn 34, Issue 7, 1995, Pages 818-820

The Chemistry of Silylenoids: Preparation and Reactivity of (Alkoxysilyl)lithium Compounds

Author keywords

silicon compounds; silylenoids

Indexed keywords


EID: 33748242214     PISSN: 05700833     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.199508181     Document Type: Article
Times cited : (103)

References (50)
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    • Aus der Chemie der Carbenoide und anderer thermolabiler Organolithium-Verbindungen
    • (a) Pertinent reviews
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  • 4
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    • Röntgenstrukturanalyse eines Alkylidencarbenoids geglückt – ein Meilenstein in der Carbenoidforschung
    • 1072–1074
    • (1993) Angewandte Chemie , vol.105
    • Maercker, A.1
  • 14
    • 84985609637 scopus 로고    scopus 로고
    • In analogy with the conventions applied for carbenoids, we will use the term “silylenoid” for a compound in which a metal atom and a leaving group are bound to the same silicon atom. The term “silylenoid character or nature” on the other hand will be used in more mechanistic sense for a species that reacts electrophilically.
  • 31
    • 84985518838 scopus 로고    scopus 로고
    • Wurtz‐type reaction of (tert‐butoxy)diphenylsilyl chloride with lithium in THF at 0 °C gave no detectable amounts of 2.
  • 32
    • 84985518833 scopus 로고    scopus 로고
    • 3SnLi, and isolated by vacuum distillation in 79% yield.
  • 35
    • 84985522512 scopus 로고    scopus 로고
    • An enhanced facile substitution of a negative leaving group in the presence of an alkyllithium compound known as the most typical hint of carbenoid nature [1].
  • 36
    • 84985519017 scopus 로고    scopus 로고
    • In the absence of TMEDA, the ratio of 8/6 was 13/87 (54% total yield). The effect of TMEDA, however, is not clear and is now under study.
  • 37
    • 0344288028 scopus 로고
    • Synthese und Struktur des Disilagermirans R2Ge(SiR2)2 und des solvensseparierten Ionenpaares [Li([12]Krone-4)2][GeR3]; R = SiMe3
    • For a recent example for inclusion of lithium cation by [12]crown‐4, see
    • (1994) Angewandte Chemie , vol.106 , pp. 121-123
    • Heine, A.1    Stalke, D.2
  • 39
    • 84985609653 scopus 로고    scopus 로고
    • 29Si NMR spectra for 9 was unsuccessful owing to the formation of a white precipitate which was insoluble even at 0 °C.
  • 40
    • 84985609677 scopus 로고    scopus 로고
    • In carbenoid chemistry, ionization of this type is sometimes called “metalassisted ionization” which involves a definite heteroatom–metal interaction, according to Walborsky et al. [1i].
  • 41
    • 84985609665 scopus 로고    scopus 로고
    • The methyl group in this model compound may not necessarily be bulkier than the lithium atom in 2, since the lithium atom must be solvated.
  • 49
    • 84985601144 scopus 로고    scopus 로고
    • Our proposal is based on the reasonable assumption that the silylenoid character of lithium(alkoxy)silylenoids can be applied to the reactivity of metal(halo)silylenoids.
  • 50
    • 84985518847 scopus 로고    scopus 로고
    • The sila‐Wittig rearrangement of (alkoxysilyl)lithium compounds, that is the organic group migration from oxygen to silicon, analogous to the Wittig rearrangement, has also been observed and will be reported in due course.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.