Payne rearrangement approach

For the synthesis of a heptanal derivative 30 (D in the retrosynthesis) from 19, we investigated two different approaches. The first approach relied on the Wittig olefination of aldehyde 25 (Scheme 3). The second was based on the attack of 2-lithio-2-methylpropionitrile (a-lithiated isobutyronitrile) [56-60] on the Payne rearrangement product 20 (Scheme 4). Our original attempt at the preparation of heptanal 30 from... 

An elegant de novo total asymmetric synthesis of (-l-)-DNJ, based on the RCM approach, was proposed by Poisson (Scheme 38). It was initiated from oxirane 193 (ee>99%), obtained by the Sharpless asymmetric epoxidation of alcohol 192 with subsequent Payne rearrangement. 

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