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Please login to access the full content or check if you have access via2.10.7.8 Method 8: Allylation of Carbonyl Compounds by Allyltris(amido)titanium(IV) Complexes
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Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 528.
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]
Meeeee 88 (η8-Meeee)eeee(eeeee)eeeeeeee(MM) Meeeeeeee; eee Meeeeeeeee Meeeeeeee ee ee Meeeeeeee(eeeee)eeeeeeee(MM) Meeeeee eeee ee Meeeeeee ee Meeeeeee eeee eee Meeeeeeee ee Meeeeeeee(eeeee)eeeeeeee(MM) Meeeeeeee eeee Meeeeeeee eee Meeeeee[888,888]
M | Meeee ee Meeeeeee | Mee |
---|---|---|
MeMe | 88:88 | [888] |
Me(MeMe)8 | 88:88 | [888] |
Me(MMe8)8 | 88:88 | [888] |
Me(MeMe)8MeMe | 88:8 | [888] |
Meeeeeeee M,M-eeeeeeeeeee eee-8-eeee eeeeeeeeee eee eeeeeeee ee eeeeeee 8-eeeeeeeeeeeeee eeeeeeeeee (e.e., 888, Meeeee 88) eeee eeee γ-eeeeeeeeeeeeeeeeee; eeee eeeeeeeeee eee eeeeee eeeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeee 8-eeeeeeeeeee.[888,888]
Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeee ee 8-Meeeeeeeeeeeee Meeeeeeeee[888,888]
Meeeeeeeeeee-8-eee eeeeeeeeeee 888 eee ee eeeeeeee ee eeeeeeeeee ee e eeeeeee eeeeeeeeee ee eee eeeeeeeeeee eeeeee eeeeeeeee.[888] Meeee- eee eeeeeeeeeeeeeeee eeeeeeee ee 888 ee eeeeeeeee eee eeeeeee eeeeeee eeeeee eeeeeeeee eeeeeeeee ee eeeeeeeeeeee eeeeee eee eeee eeeeeeeeeee eeeeeeeeeeee eeeeeeee (Meeeee 88).[888]
Meeeee 88 Meeee- eee Meeeeeeeeeeeeeee Meeeeeeee ee Meeeeeeee(eeeee)eeeeeeee(MM) Meeeeeeee eeee Meeeeeeee eee Meeeeee[888]
References
[283] | Meeee, M.-M.; Müeeee, M. M., M. Meeeeeeee. Meee., (8888) 88, 888. |
[284] | Meeeeee, M.; Meeeeee, M., Meee. Meee Meee, (8888) 88, 8888. |
[285] | Meeee, M. M.; Meeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[286] | Meeeee, M.; Meeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[287] | Meeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[288] | Meeee, M.; Meeeeeee, M.; Meeeee, M. M.; Meeeee, M.; Meeeeeeee, M. M. M., Meeee. Meee., (8888), 88, 888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88-8, 888.
- 8.Meeeee-Meee, (8888) M 88e, 8888.