Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 524.

Reaction of a dichlorobis(η5-cyclopentadienyl)titanium(IV) (‌78‌)/trimethylaluminum mixture (1:4) with vinyl halides or vinyl esters ‌139‌ and subsequent reaction with aldehydes affords homoallyl alcohols ‌141‌ via (η1-allyl)titanium complex ‌140‌ (‌Scheme 70‌). The formation of ‌140‌ is suggested to proceed via a titanacyclobutane, with subsequent elimination of the halogen or alkoxy group. The reaction of esters with 3 equivalents of [Ti(Cp)2Cl2] (‌78‌) and trimethylaluminum affords vinyl esters by Tebbe methylenation, followed by the formation of σ-allyltitanium complexes.[‌275‌]

‌Meeeee 88‌ Meeeeeeeeee ee Meeeeeeeeee Meeeeeee eee (η8-Meeee)eee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) Meeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeeeeee-8-ee-8-ee (‌888‌, M8 = M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

Me e eeee ee [Me(Me)8Me8] (‌88‌; 888 ee, 8.8 eeee) ee eeeeeee (8 eM) eee eeeee 88% Me8Me (8.8 eM, 8.8 eeee) ee eeeeeee ee ee; eee eeee eee eeeeeee eee 8 e ee eee eeee eeeeeeeeeee. M eeee ee M8M=M(Me)Me (‌888‌, M = Me, M8 = Me; 888 ee, 8.8 eeee) ee MMM eee eeeee ee eee eeeeeee ee 8°M, eee eee eeeeeeeee eeeeeee eee eeeeeee eee 8.8 e ee ee, eee eee 88 e ee 88°M. Meeee eee eeeeeee eee eeeeee ee 8°M, e eeee ee MeMMM (888 ee, 8.8 eeee) ee MMM (8 eM) eee eeeee eee eee eeeeeee eee eeeeeee ee ee eee 8 e. Meeee eeeeeeee ee 8 M MeMM eeeee eee eeeeeee, eee eeeeeee eee eeeeeeee eeeeeee e Meeeee eee, eee eee eeeeeeee eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee eee eeeee (MeMM8). Mee eeeeeeee Me8M eeee eee eeeeeeeeeeee ee eeeeeee ee eeeee ee eeee e eeeee eee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8–8:8) ee eeee e eeeeeeeee eee; eeeee: 888 ee (88%).

References