Rj. Van Haaren et al., On the influence of the bite angle of bidentate phosphane ligands on the regioselectivity in allylic alkylation, EUR J INORG, (8), 1999, pp. 1237-1241
The natural bite angle of bidentate phosphane ligands influences the isomer
distribution (syn and anti) in (1-methylallyl)(bisphosphane)Pd OTf complex
es. It was found (P-31- and H-1-NMR studies) that the syn/anti ratio change
s from 12 (dppp) to 1.3 (sixantphos). Molecular orbital calculations [PM3(t
m) level] indicate that for ligands inducing a large bite angle, the phenyl
rings of the ligand embrace the allyl moiety thus influencing the syn/anti
ratio. This bite-angle effect on the syn/anti ratio is transferred to the
regioselectivity in stoichiometric allylic alkylation. Ligands inducing lar
ge bite angles direct the regioselectivity towards the formation of the bra
nched product 2. Catalytic alkylation of (E)-2-butenyl acetate showed that
for ligands with a small bite angle the regioselectivity of the catalytic a
nd stoichiometric alkylation are in good agreement. This correspondence is
worse for ligands with a larger bite angle, which is rationalised in terms
of the relative rates of syn/anti isomerisation and alkylation. The ligand
with the largest bite angle (sixantphos) gives the most active catalytic sp
ecies.