Aza--Wittig Rearrangement

In the laboratory of J.C. Anderson, the total synthesis of (+)-kainic acid was accomplished relying on a route that utilized an aza-[2,3]-Wittig rearrangement as the key step to install the correct relative stereochemistry between C2 and C3. The C4 stereocenter was established via an iodolactonization reaction. 

Investigations by J. Oh showed that the cycloaddition of dichloroketene to glucal followed by Baeyer-Villiger oxidation afforded a bicyclic y-lactone, an a-D-C-glucoside, which was further transformed to a C1-methyl glucitol derivative.  

In the laboratory of T.K.M. Shing, the functionalized CD-ring of Taxol was synthesized in 21 steps starting out from 

An unexpected rearrangement was observed in the peroxytrifluoroacetic acid-mediated Baeyer-Villiger oxidation of 

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The aza-Wittig rearrangement in synthesis and transformations of N-hetero-cycles 97S497. 

Sigmatropic rearrangements of anions of (V-allyl amines have also been observed and are known as aza-Wittig rearrangements.291 The reaction requires anion stabilizing substituents and is favored by (V-benzyl and by silyl or sulfenyl substituents... 

Aza-Wittig rearrangements are grouped according to substrate structure in Table 6. 

Review articles have addressed advances in photochemical generation and reactions of carbanions,165 the [l,2]-WMg rearrangement stereochemistry and synthetic application,167 and the aza-Wittig rearrangement.168... 

A review which describes recent developments of the aza-Wittig rearrangement and its application in alkaloid synthesis has appeared.212 The aza-[2,3]-Wittig rearrangement (157) (158) has been shown to be accelerated by the incorporation of certain... 

Aza-Wittig rearrangement in the acyclic series are harder to control.141 The most reliable turn out to be those of allyl amides such as 192 in which the allyl group bears a (3-silyl substituent, whose function is to stabilise the anionic transition state of the reaction.142 143... 

An aza-Wittig rearrangement is also known There are no OS references, but see OS VIII, 501, for a related reaction. 

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