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the desired products in high yields and with good enantioselectivi-
ties. There was no significant influence of the substituents at the
ortho-, meta- or para-positions (entries 5–10). Similarly,
electron-withdrawing substituents such as p-chlorobenzaldehyde
on the aromatic aldehyde also afforded good enantioselectivity
and reactivity (entry 11). On the other hand, aliphatic aldehydes
and sterically hindered aldehydes only gave moderate enantioselec-
tivities (entries 12–14).
A plausible mechanism is shown in Scheme 1 for the asymmet-
ric silylcyanation of aldehydes catalyzed by complex 4, although it
does not explain the higher selectivity when compared with other
oxovanadium species 3, and 5–8. Complex 4 was expected to be a
hexa-coordinated vanadium species.15 It formed another hexa-
coordinated vanadium species 9 in the presence of the aldehyde
and TMSCN, followed by cyanation of the aldehyde with an attack
of the penta-coordinate silicon intermediate16 that was generated
by the reaction of TMSCN with TBAF on the Re-face. The vanadium
species 10 was further replaced by an aldehyde to give the cyana-
tion product and regenerated vanadium species 9. The free alde-
hyde group of the vanadium species 9 did not react with TMSCN,
presumably due to deactivation by the ortho-oxy anion.
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3. Conclusion
In conclusion, we have synthesized a new vanadium species,
with tridentate ligands, from VOSO4 with substituted salicylalde-
hydes and inexpensive (S)-valine, and applied it in the asymmetric
silylcyanation of aldehydes with up to 90% enantioselectivity being
achieved.
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Acknowledgement
We thank the National Science Council of the Republic of China
(Taiwan) for the financial support of this work.
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