Treatment of Ti(O-i-Pr)(4) with 2 equiv of i-PrMgX (X = Cl or Br) prov
ides (eta(2)-propene) Ti(O-i-Pr)(2) in essentially quantitative yield.
This new low-valent titanium complex nicely acts as a versatile titan
ium (II) equivalent to effect the following unique transformations. Th
us, alkynes afforded titanium-alkyne complexes which, in turn, react w
ith aldehydes, ketones, or imines to furnish the corresponding additio
n products. Allylic or propargylic compounds such as halides and alcoh
ol derivatives gave allylic- or allenylic titanium species, which coul
d be utilized in chemo-and diastereoselective reactions with carbonyl
compounds. While acetylenic esters resulted in an intramolecular nucle
ophilic acyl substitution (INAS) reaction to provide unsaturated keton
es, olefinic ones furnished cyclopropanols. 1,6- or 1,7-Dienes, enynes
, and diynes underwent cyclometallation to give dialkoxytitanacycles,
which show some distinctive reactivities among the metallacycles of ea
rly transition metal complexes. A few applications to natural product
synthesis by taking advantage of these methods are also illustrated.