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Abstract: Sm/TiCl₄ system could well integrate the high reactivity of samarium(II) and high deoxygenation capacity of low valent titanium within one system. In this paper, the intermolecular and intramolecular reductive coupling reactions of ketones with esters mediated by metallic samarium (Sm) and a catalytic amount of titanium tetrachloride (TiCl₄) were successfully developed. A series of substituted ketones and cyclic β-keto-esters were prepared in moderate to good yields under reflux and neutral conditions.

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