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Please login to access the full content or check if you have access via2.10.7.5 Method 5: (η1-Allyl)bis(isopropoxy)titanium(IV) Complexes by Reaction of Low-Valent Titanium Complexes with Allylic Halides, Acetates, Carbonates, Phosphates, Sulfonates, or Aryl Ethers
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Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 525.
Sato and co-workers report the reaction of divalent titanium complex 142, prepared from [Ti(OiPr)4] or [TiCl(OiPr)3] and 2 equivalents of isopropylmagnesium bromide, with allyl alcohol derivatives that have a leaving group at the allylic position, such as allylic halides, acetates, carbonates, phosphates, sulfonates, or aryl ethers (Scheme 71). A ligand exchange reaction followed by β-elimination gives [Ti(η1-allyl)(OiPr)2X] complexes 143 in excellent yields. The synthesis can be carried out starting with readily available allylic alcohol derivatives and an inexpensive titanium alkoxide.[276–278] The method allows the preparation of σ-allyltitaniums that have functional groups such as esters and halides. The reaction with seven-, eight-, and nine-membered cyclic allylic halides or carbonates affords the corresponding cyclic allyltitaniums.[277] Allyltitanium complex 144, prepared from 1-vinylcyclopropyl carbonate and a titanium(II)–alkene complex, reacts highly selectively with electrophiles at the less substituted carbon to give alkylidenecyclopropane derivatives.
Meeeee 88 Meeeeeeeeee eee Meeeeeee ee η8-Meeeeeeeeeeee(MM) Meeeeeeee[888–888]
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Meeeee 88 Meeeeeeeeee ee η8-Meeeeeeeeeeee(MM) Meeeeeeee[888,888]
Meeeeeeeeeee Meeeeeeee
8-Meeeeeeee-8-ee-8-ee (888); Meeeeee Meeeeeeee:[888]
Me e eeeeeee ee [Me(MeMe)8] eee 8-eeeeeeeee-8-eee ee eeee-8-ee-8-ee ee Me8M eee eeeee eMeMeMe (8 eeeee) ee −88°M. Meeee eee eeeeeee eee eeeeeee eee 8 e ee −88 ee −88°M, MeMMM eee eeeee eee eee eeeeeee eee eeeeeee eee 88 eee ee eeee eee eeeeeee; eeeee: 88%.
References
[276] | Meeeeeee, M.; Meeeeeee, M.; Meeeeee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[277] | Meeeeee, M.; Mee, M.; Meee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[278] | Meeeeeee, M.; Meee, M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee., Me. Meee., (8888) 88, 8888. |
[279] | Meee, M.; Meeeeeee, M.; Meeeeee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
[280] | Meeeeeee, M.; Me, M. M.; Meeeeeee, M.; Meee, M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88e, 8888.
- 8.Meeeee-Meee, (8888) M 88e, 8888.