Silicon-Oxygen Heterocycles from Thermal, Photochemical, and Transition-Metal-Catalyzed Decomposition of α-(Alkoxysilyl and Alkenyloxysilyl)-α-diazoacetates
✍ Scribed by Gerhard Maas; Fred Krebs; Thorsten Werle; Volker Gettwert; Ruth Striegler
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 317 KB
- Volume
- 1999
- Category
- Article
- ISSN
- 1434-193X
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✦ Synopsis
Photolysis of (ethoxy)silyl-, (propyloxy)silyl-, and (isopro-oxasiloles 4b-d, which are likely to be formed on a pyrazoline rather than a carbene route. For (3-butenyloxysilyl)diazo-pyloxy)silyl-substituted diazoacetates 1a-c leads to tetrahydro-1,2-oxasiloles 2a-c by intramolecular C-H acetate 3f, all modes of decomposition generate the 3-oxa-2silabicyclo[4.1.0]heptane system 7.
Fluoride-induced insertion of a carbene intermediate. Photochemical or catalytic decomposition of (allyloxysilyl)diazoacetates 3a-e cleavage of the bicyclic systems 5b-d provides trans-2hydroxyalkyl-1-cyclopropanecarboxylates 9 diastereospeci-results in intramolecular cyclopropanation which provides 3oxa-2-silabicyclo[3.1.0]hexane systems 5a-e. In contrast, the fically. thermal reaction of 3b-d gives rise to 2,5-dihydro-1,2ane, resulted in a clean 1,4-CϪH insertion to form a 1,2-si-Decomposition of (Alkoxysilyl)diazoacetates 1a؊c