An Efficient Stereoselective Synthesis of Substituted 1,3-Dienes

Abstract

A stereoselective synthesis of substituted 1,3-dienes has been developed which utilises an Ireland-Claisen rearrangement/silicon-mediated fragmentation sequence. This sequence has been designed to introduce remote centres of asymmetry as well as stereo­defined diene systems, and its application to an aziridine ­system is also described.

Key words

aziridine - Ireland-Claisen rearrangement - Sharpless asymmetric epoxidation - silicon-mediated fragmentation

References

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1

New address: Kyungsoo Oh, Department of Chemistry, University of Pennsylvania, 231S, 34th Street, Philadelphia, PA 19104, USA.

13

A single crystal of 6a of 3,5-dinitrobenzoyl derivative was obtained and the selectivity of 5b and 6b were made from analogy of our Galbonolide study.

16

Stereoselective epoxide opening using Ti(i-PrO)₄ (Scheme [5] ).

17

BF₃·OEt₂ initiated fragmentation of 9a followed by dehydration of 10a to give 9d (Scheme [6] ).

19

Aziridine opening by chloride anion in esterification conditions (Scheme [7] ).

21

Conditions using LHMDS and TMSCl-Et₃N did not yield any identifiable product.