Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.

Issue 20, 2005
Previous Article Next Article

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

Author affiliations


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

Back to tab navigation

Article information

29 Jul 2005
22 Aug 2005
First published
12 Sep 2005

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

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

Social activity

Search articles by author