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Please login to access the full content or check if you have access via Method 8: Allylation of Carbonyl Compounds by Allyltris(amido)titanium(IV) ­Complexes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032528.

Allyltitanium complexes 149 (R1=R2=H, Me; R3=Me, Et) (Scheme 75) have been prepared by Grignard reactions. Diethylamido compounds 149 (R3=Et) are thermally stable. The allyl groups are σ-bonded and exhibit dynamic behavior in the 1H NMR spectra between 65 and 80°C.[‌283‌] [Ti(η3-allyl)(NR32)3] complexes 149 are capable of discriminating between aldehydes and ketones. Because the allyl ligand is less nucleophilic than the amido ligands,[‌284‌] complexes 149 can be used as ketone-selective reagents through first aminating with the more nucleophilic amide, followed by allylation (Scheme 75).[‌285‌]

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