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| Title
| - Nitrile Anion Cyclization with Epoxysilanes Followed by BrookRearrangement/Ring-Opening of Cyclopropane Nitriles/Alkylation
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| Abstract
| - The reaction of δ-silyl-γ,δ-epoxypentanenitrile derivatives 9−12 with a base and an alkylating agentaffords (Z)-δ-siloxy-γ,δ-unsaturated pentanenitrile derivatives via a tandem process that involvesthe formation of a cyclopropane derivative by epoxy nitrile cyclization followed by Brookrearrangement and an anion-induced cleavage of the cyclopropane ring. Exclusive formation of a(Z)-derivative from trans-epoxides is explained by the reaction pathway that involves a backsidedisplacement of the epoxide by the α-nitrile carbanion and the O−Si bond formation followed byconcerted processes involving Brook rearrangement and the anti-mode of eliminative ring fissionof the cyclopropane from the rotamer 19. The fact that (E)-isomers are exclusively obtained fromcis-epoxides and α-cyclopropyl-α-silylcarbinol derivative 26 provides experimental support for theproposed pathway.
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