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Synthesis 2010(18): 3105-3112  
DOI: 10.1055/s-0030-1257869
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of (R)-Coniine and (S)-Coinicine via Organocatalytic α-Aminoxyl­ation of an Aldehyde

Nagendra B. Kondekar, Pradeep Kumar*
Division of Organic Chemistry, National Chemical Laboratory, Pune 411008, India
Fax: +91(20)25902629; e-Mail: pk.tripathi@ncl.res.in;
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Publication History

Received 22 April 2010
Publication Date:
22 July 2010 (online)

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Abstract

A short and efficient synthesis of the indolizidine alkaloid (S)-coinicine has been achieved using organocatalytic sequential α-aminoxylation and Horner-Wadsworth-Emmons olefination of an aldehyde catalyzed by l-proline. Similarly, a common organocatalytic α-aminoxylation route has been developed for the asymmetric synthesis of both (R)-coniine and (S)-coinicine.

Key words

synthesis - organocatalysis - sequential reactions - proline - hemlock alkaloids

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12

The enantiomeric excess (95% ee) was calculated using Mosher analysis by converting alcohol 8 into the monobenzylated alcohol 23 (Figure  [²] ) and then derivatizing alcohol 23 as its Mosher ester.

13

The enantiomeric excess of 18 (95% ee) was calculated using Mosher analysis by derivatizing alcohol 18 as its Mosher ester.