C(sp3)−H Oxidative Addition and Transfer Hydrogenation Chemistry of a Titanium(II) Synthon: Mimicry of Late‐Metal Type Reactivity
作者： J. Rolando Aguilar-Calderón , Alejandro J. Metta-Magaña , Bruce Noll , Skye Fortier
关键词: Synthon 、 Dehydrogenation 、 Cyclohexene 、 Oxidative addition 、 Photochemistry 、 Metallacycle 、 Medicinal chemistry 、 Reactivity (chemistry) 、 Transfer hydrogenation 、 Chemistry 、 Isopropyl
摘要: Two-electron reduction of the TiIV compound (ketguan)(ImDippN)Ti(OTf)2 (3) gives arene-masked complex (ketguan)(η6-ImDippN)Ti (1) in excellent yield. Upon standing solution, 1 converts to a metallacycle (4) through dehydrogenation pendant isopropyl group. Spectroscopic evidence shows this transformation initially proceeds via oxidative addition C(sp3)−H bond and can be reversed upon exposure 4 H2. Interestingly, treatment with cyclohexene cyclohexane titanium-mediated transfer hydrogenation reaction, process that extended catalytically hydrogenate other unsaturated hydrocarbons under mild conditions. These results, rare for early-metals, suggest possesses chemical characteristics reminiscent noble, late-metals.
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