(Z)-Selective Takai olefination of salicylaldehydes.
The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E)-selectivity; however, herein we report the highly (Z)-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
Stephen M
SM
Geddis
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
Caroline E
CE
Hagerman
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
Warren R J D
WRJD
Galloway
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
Hannah F
HF
Sore
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
Jonathan M
JM
Goodman
Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge, CB2 1EW, UK.
David R
DR
Spring
Takai olefination; alkenyl iodides; salicylaldehydes; stereoselectivity; transition state