• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.453-459
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• 2003

(Pyridine)(tetrahydroborato)zinc complex, $[Zn(BH_4)_2(py)]$, as a stable white solid, was prepared quantitatively by complexation of an equimolar amount of zinc tetrahydroborate and pyridine at room temperature. This reagent can easily reduce variety of carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and a, β-unsaturated carbonyl compounds to their corresponding alcohols in good to excellent yields. Reduction reactions were performed in ether or THF at room temperature or under reflux conditions. In addition, the chemoselective reduction of aldehydes over ketones was accomplished successfully with this reducing agent.

• Clean Technology
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• v.29 no.2
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• pp.79-86
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• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.