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Synfacts 2006(8): 0802-0802  
DOI: 10.1055/s-2006-941915
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Claisen Rearrangements Enabled by Asymmetric Di(allyl) Ether Synthesis

Contributor(s): Hisashi Yamamoto, Matthew B. Boxer
S. G. Nelson*, K. Wang
University of Pittsburgh, USA
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Publication History

Publication Date:
21 July 2006 (online)

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Significance

The authors describe a nice protocol for aliphatic Claisen rearrangements from very simple starting materials. The reaction sequence begins with the enantioselective synthesis of di(allyl) ethers by MIB-catalyzed addition of Et2Zn to α,β-unsaturated aldehydes. The ethyl zinc alk­oxide was transformed into a zinc carboxylate with AcOH, which underwent O-allylation with allyl acetate under Pd(0) catalysis. This di(allyl) ether was subjected to the olefin isomerization-Claisen rearrangement conditions, which involves [Ir(PCy3)3]+/PPh3 catalysis.