Treatment of a titanatrane complex with trimethylsilyl chloride and magnesium powder in tetrahydrofuran generated a low‐valent titanium species. This species catalyzed the radical ring opening of epoxides and oxetanes to produce the corresponding less substituted alcohols. The reagent also catalyzed the deallylation and depropargylation of allylic and propargylic ethers, respectively, to provide the parent alcohols.magnified image

The first examples of the C-O bond cleavage of various oxetanes at the 2-position using low valent titanium alkoxides, generated in situ from the titanatrane complex, Mg, and TmsCl, are presented. Addition of 1,4-cyclohexadiene is beneficial. The catalytic system is also effective in the deallylation and depropargylation of ethers. -(TAKEKOSHI, N.; MIYASHITA, K.; SHOJI, N.; OKAMOTO*, S.; Adv. Synth. Catal. 355 (2013) 11-12, 2151-2157, http://dx.