Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >...

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Published inOrganic & biomolecular chemistry Vol. 7; no. 12; pp. 2604 - 2611
Main Authors Davies, Stephen G., Garner, A. Christopher, Nicholson, Rebecca L., Osborne, James, Roberts, Paul M., Savory, Edward D., Smith, Andrew D., Thomson, James E.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.01.2009
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ORGANIC-SYNTHESIS
ENANTIOMERICALLY PURE
(-)-ISOIRIDOMYRMECIN
STEREOCHEMICAL CONTROL
ASYMMETRIC INDUCTION
CRYSTAL-STRUCTURE
AMINO-ACIDS
ACETAL
STEREOSELECTIVE-SYNTHESIS
AUXILIARY
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Summary:The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >90% de under the "matched" control of both stereogenic centres. Rearrangement of the "mismatched" diastereomeric (3R,4E,alpha R)-substrates proceeds with low diastereoselectivity. The substrate scope of the doubly diastereoselective rearrangement of the "matched" substrates in which two new stereogenic centres are created has been delineated.
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ISSN:1477-0520
1477-0539
DOI:10.1039/b902753j