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Issue 20, 2005
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Chirality transfer in the aza-[2,3]-Wittig sigmatropic rearrangement

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Abstract

The aza-[2,3]-Wittig sigmatropic rearrangements of substrates derived from enantiomerically pure alanine, valine and serine with phenyl and ester anion stabilising groups were investigated for their efficiency in chirality transfer. It was found that a methyl substituent at the stereogenic centre of the rearrangement precursors was inadequate to control the alkene stereoselectivity and enantioselectivity of the rearrangement. Ester stabilised anions of valine and serine derivatives were the most successful with up to 66% yield, 14 : 1 alkene (E)-stereoselection and 88% chirality transfer. A limitation to the steric bulk of the stereogenic centre was noted in that the substituent has to be bulky enough to dictate alkene stereoselection, but not too large to compromise the directing effect of the activating phenyldimethyl silyl substituent on the anion stabilising group. Experimental evidence suggested a possible complimentary coordinating effect of an O–MOM serine substituent, which may assist alkene stereoselectivity and enantioselectivity.

Graphical abstract: Chirality transfer in the aza-[2,3]-Wittig sigmatropic rearrangement

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Article information


Submitted
29 Jul 2005
Accepted
22 Aug 2005
First published
12 Sep 2005

Org. Biomol. Chem., 2005,3, 3734-3748
Article type
Paper

Chirality transfer in the aza-[2,3]-Wittig sigmatropic rearrangement

J. C. Anderson, J. G. Ford and M. Whiting, Org. Biomol. Chem., 2005, 3, 3734
DOI: 10.1039/B510756C

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