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Anionic 1,4 O→C silyl rearrangements

✍ Scribed by Christoph Rücker

Book ID
104233802
Publisher
Elsevier Science
Year
1984
Tongue
French
Weight
215 KB
Volume
25
Category
Article
ISSN
0040-4039

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✦ Synopsis

y-Silyloxy-alkyl phenyl thioethers are transformed into y-silylalcohols by treatment with lithium di-tert-butylbiphenyl.

In the preceding communication 1) the 1,3 O--C migration of silyl groups in carbanions made by deprotonation of ketone silyl enol ethers was described. In the present note similar anionic 1,4 0-C silyl migrations are reported.

Anionic 1,4 C+O silyl shifts are known to occur when epoxides are opened by methyllithiums substituted by a TMS and at least one other strongly anion stabilizing group 2,X) .

📜 SIMILAR VOLUMES

Anionic rearrangements starting with 1-l
Anionic rearrangements starting with 1-lithio-2-propynyl silyl ethers a route to (β-trimethylsilylvinyl) silyl ketones
✍ K.J.H. Kruithof; G.W. Klumpp 📂 Article 📅 1982 🏛 Elsevier Science 🌐 French ⚖ 110 KB

The title compounds undergo silyl-Wittig rearrangement at low temperature and lead to allenolates at room temperature. The mobility of both silicon and lithium in the system 2\_\_\_\_ -3-4 forms the basis of syntheses of siloxyallenes 5 (and the corresponding cr,B-unsaturated ketones) from silyl ke