On the origin of high E selectivity in the Wittig reaction of stabilized ylides: importance of dipole-dipole interactions.
The salt-free Wittig reaction of stabilized ylides Ph3PCHCO2Me 1 and (MeO)3PCHCO2Me 2 has been investigated using DFT method including solvation. This analysis shows that TS structures and E/Z selectivity in the phosphine stabilized ylide 1, which gives high E selectivity with PhCHO, are predominantly controlled by a dipole-dipole interaction between the two reactants at the TS (as well as the well-known 1,2 and 1,3 steric interactions). The surprisingly different behavior of the phosphite ylide 2, which gives only 69:31 E/Z ratio with PhCHO, is accounted for by its much smaller overall dipole. The introduction of this new parameter (dipole-dipole interactions), which has not previously been invoked in discussions of this important reaction, accommodates all the experimental observations relating to selectivity in the Wittig reaction of stabilized ylides under salt-free conditions.
Robiette
Raphaël
R
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
Richardson
Jeffery
J
Aggarwal
Varinder K
VK
Harvey
Jeremy N
JN