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2.10.9.6 Method 6: Titanacycles from Ligand Exchange Reactions of Titanacyclopentanes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032547.

Ligand exchange between titanacyclopentane 184 and an externally added alkene leads to a new titanacyclopentane (Scheme 102).[‌335‌] A titanacyclopentadiene results from the reaction between titanacyclopentane 189 and an alkyne (Scheme 102). Ligand exchange between tetraethyltitanacyclopentadiene 187 and alkenes results in titanacyclopentanes 160 (Scheme 102). The resulting titanacyclopentanes 160 undergo coupling reactions with a variety of unsaturated compounds (Scheme 103).[‌313‌] Monoprotonation with water gives a 2,3-dimethylbutyltitanium complex 208.[‌313‌] The reaction with benzophenone or an imine results in ring expansion. However, imines, particularly aromatic imines, form homocoupling products.

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