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Activation of methylenetriphenylphosphorane by reaction with t-butyl- or sec-butyllithium

✍ Scribed by E.J. Corey; Jahyo Kang; Keith Kyler

Book ID
104222338
Publisher
Elsevier Science
Year
1985
Tongue
French
Weight
249 KB
Volume
26
Category
Article
ISSN
0040-4039

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✦ Synopsis

Experimental details are provided to support a previous report that c+methylenetriphenylphosphorane ( &, ) may be activated for reaction with unreactive substrates such as epoxides and hindered ketones by o-metallation to 2_.

It has recently been discovered in this laboratory' that methylenetriphenylphosphorsne (L ) reacts with t_butyllithium or see-butyllithium to form a more reactive reagent which is capable of transforming certain substsnces which do not react with methylenetriphenylphosphorane to products that could be explained by the formulation of the reagent as cY-lithiomethylenetriphenylphosphorane

( 2 ). Thus fenchone ( 3~ was methylenated to form 2 (870/o yield) by the lithiated ylide reagent whereas there was no appreciable conversion of 2 to 2 under the same conditions using methylenetriphenylphosphorsne as the reagent. Cyclopentene oxide was attacked by the reagent to generate a new ylide ( 6_ ) which underwent further coupling with benzaldehyde to form the E homoallylic alcohol 2 in 65% yield. Control experiments showed that cyclopentene oxide was unreactive to methylenetriphenylphosphorane ( l_) under the same conditions.

πŸ“œ SIMILAR VOLUMES

Direct conversion of amines to the corre
Direct conversion of amines to the corresponding halides by deamination with t-butyl thionitrite or t-butyl thionitrate and copper(II) halides
✍ Yong H. Kim; Kōichi Shinhama; Shigeru Oae πŸ“‚ Article πŸ“… 1978 πŸ› Elsevier Science 🌐 French βš– 197 KB

We reported recently that both t-butyl thionitrite')and t-butyl thionitrate')can be prepared simply by treating t-butyl mercaptan with dinitrogen tetraoxide. We now have found that various arylamines reacted readily with either t-butyl thionitrite or t-butyl thionitrate and copper(I1) halides under