Synthetic Reactions Using Low‐valent Titanium Reagents Derived from Ti(OR)4 or CpTiX3 (X = O‐i‐Pr or Cl) in the Presence of Me3SiCl and Mg

In the presence of Me₃SiCl, Ti(OR)₄ or CpTiX₃ (X = O‐i‐Pr or Cl) is reduced by Mg powder in THF to gradually generate a specific low‐valent titanium (LVT) species that mediates several synthetic reactions. The LVT‐catalyzed C–O bond‐cleaving reactions of allyl and propargyl ethers and esters generate parent alcohols and carboxylic acids, respectively. O‐allyl and propargyl carbamates are also readily deprotected by the LVT to afford parent amines. In addition, the respective reductive N–S or O–S bond cleavage of sulfonamides or sulfonyl esters mediated by the LVT was developed as a novel facile deprotection method. The reagent catalyzes intra‐ and intermolecular alkyne or alkyne/nitrile cycloaddition to produce substituted benzenes and pyridines, while epoxides and oxetanes are reduced to alcohols via an LVT‐mediated homolytic ring opening. The McMurry coupling of aryl aldehydes and ketones proceeds with the LVT under homogeneous and mild reaction conditions and is effective for the polymerization of aromatic dialdehydes, generating conjugated polymers. Finally, imino‐pinacol coupling of imines is mediated by the LVT to provide 1,2‐diamines.