Hydroformylation of Alkenes in a Planetary Ball Mill: from Additive-Controlled Reactivity to Supramolecular Control of Regioselectivity,Angewandte Chemie International Edition

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Hydroformylation of Alkenes in a Planetary Ball Mill: from Additive-Controlled Reactivity to Supramolecular Control of Regioselectivity
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2017-07-24 06:17:34 , DOI: 10.1002/anie.201705467
Kévin Cousin ₁ , Stéphane Menuel ₁ , Eric Monflier ₁ , Frédéric Hapiot ₁

Affiliation

The Rh-catalyzed hydroformylation of aromatic-substituted alkenes is performed in a planetary ball mill under CO/H₂ pressure. The dispersion of the substrate molecules and the Rh-catalyst into the grinding jar is ensured by saccharides: methyl-α-d-glucopyranoside, acyclic dextrins, or cyclodextrins (CDs, cyclic oligosaccharides). The reaction affords the exclusive formation of aldehydes whatever the saccharide. Acyclic saccharides disperse the components within the solid mixture leading to high conversions of alkenes. However, they showed typical selectivity for α-aldehyde products. If CDs are the dispersing additive, the steric hindrance exerted by the CDs on the primary coordination sphere of the metal modifies the selectivity so that the β-aldehydes were also formed in non-negligible proportions. Such through-space control via hydrophobic effects over reactivity and regioselectivity reveals the potential of such solventless process for catalysis in solid state.

中文翻译：

行星式球磨机中烯烃的加氢甲酰化：从加成控制的反应性到区域选择性的超分子控制

芳族取代烯烃的Rh催化加氢甲酰化反应是在行星式球磨机中于CO / H ₂压力下进行的。糖类：甲基-α- d可确保底物分子和Rh催化剂分散到研磨罐中-吡喃葡萄糖苷，无环糊精或环糊精（CD，环状低聚糖）。无论糖是什么，该反应均能形成醛的排他性。无环糖将组分分散在固体混合物中，导致烯烃的高转化率。然而，它们显示出对α-醛产物的典型选择性。如果CD是分散添加剂，则CD在金属的初级配位球上施加的空间位阻会改变选择性，从而也以不可忽略的比例形成β-醛。通过对反应性和区域选择性的疏水作用的这种贯穿空间的控制揭示了这种无溶剂方法在固态催化中的潜力。

更新日期：2017-07-25

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