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Silicon-directed beckmann fragmentation. Catalytic cleavage of cyclic β-trimethylsilylketoxime acetates with trimethylsilyl trifluoromethanesulfonate

✍ Scribed by Hisao Nishiyama; Koji Sakuta; Noriyuki Osaka; Kenji Itoh


Book ID
104221573
Publisher
Elsevier Science
Year
1983
Tongue
French
Weight
204 KB
Volume
24
Category
Article
ISSN
0040-4039

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✦ Synopsis


Cyclic (E)-B-trimethylsilylketoxime acetates were effectively cleaved by a catalytic action of trimethylsilyl trifluoromethanesulfonate to give the corresponding unsaturated nitriles. The fragmentation in the Beckmann rearrangement is completely controlled and directed by trimethylsilyl group to lead regio-and stereospecific formation of the double bond.

Under the same reaction condition, (Z)-isomers of the 8-IMS-oxime acetates were almost recovered (-90%).