Hf-based metal–organic frameworks as acid–base catalysts for the transformation of biomass-derived furanic compounds into chemicals,Green Chemistry

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Hf-based metal–organic frameworks as acid–base catalysts for the transformation of biomass-derived furanic compounds into chemicals
Green Chemistry ( IF 9.3 ) Pub Date : 2018-06-13 , DOI: 10.1039/c8gc00806j
Sergio Rojas-Buzo _{1,

2,

3,

4,

5} , Pilar García-García _{1,

2,

3,

4,

5} , Avelino Corma _{1,

2,

3,

4,

5}

Affiliation

Hf-based metal–organic frameworks (MOFs) are reported here as heterogeneous catalysts for the highly selective and efficient cross-aldol condensation of biomass-derived furanic carbonyls with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled acetone confirm that acid–base pairs in the MOF framework promote the soft enolization of acetone through α-proton abstraction. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity, which could be regained by Soxhlet extraction. Furthermore, Hf-MOF-808 maintains activity in the presence of frequent contaminants in biomass-based molecules such as water and acids, unlike traditional base catalysts. The generality of the procedure was shown by accomplishing the transformation with aromatic and aliphatic aldehydes with acetone as the enolizable component to yield the corresponding α,β-unsaturated methyl ketones which are versatile synthons in fine chemistry. Hf-MOF-808 could also be used in the one-pot synthesis of allylic alcohols by the sequential aldol condensation reaction to yield the α,β-unsaturated methyl ketone and the subsequent Meerwein–Ponndorf–Verley reduction of the carbonyl by a simple solvent exchange from acetone to isopropyl alcohol. Furthermore, Hf-MOF-808 was decorated with palladium particles and the resultant material could be used in the one-pot aldol condensation and subsequent highly selective double bond reduction.

中文翻译：

基金属有机框架作为酸碱催化剂，用于将生物质衍生的呋喃化合物转化为化学物质

在此报道了基于的金属-有机骨架（MOF），作为异质催化剂，可在温和的反应条件下，以接近定量的收率，高度选择性和高效地将生物质衍生的呋喃羰基化合物与丙酮进行交叉羟醛缩合。用同位素标记的丙酮进行的NMR研究证实，MOF骨架中的酸碱对通过α-质子抽象促进了丙酮的软烯醇化。Hf-MOF-808催化剂可循环使用几次，但催化活性仅略有下降，可通过索氏提取回收。此外，与传统的碱催化剂不同，Hf-MOF-808在基于生物质的分子（例如水和酸）中存在频繁的污染物的情况下仍能保持活性。通过用芳族和脂族醛以丙酮作为可烯醇化的组分完成转化，得到相应的α，β-不饱和甲基酮，可以证明该方法的通用性，该酮在精细化学中是通用的合成子。Hf-MOF-808还可以通过顺序的羟醛缩合反应用于一锅法合成烯丙醇，以生成α，β-不饱和甲基酮，随后通过简单的溶剂将Meerwein-Ponndorf-Verley还原为羰基从丙酮换成异丙醇。此外，Hf-MOF-808饰有钯颗粒，所得材料可用于一锅羟醛缩合反应和随后的高选择性双键还原反应。β-不饱和甲基酮，在精细化学中是通用的合成子。Hf-MOF-808还可以通过顺序的羟醛缩合反应用于一锅法合成烯丙醇，以生成α，β-不饱和甲基酮，随后通过简单的溶剂将Meerwein-Ponndorf-Verley还原为羰基从丙酮换成异丙醇。此外，Hf-MOF-808饰有钯颗粒，所得材料可用于一锅羟醛缩合反应和随后的高选择性双键还原反应。β-不饱和甲基酮，在精细化学中是通用的合成子。Hf-MOF-808还可以通过顺序的羟醛缩合反应用于一锅法合成烯丙醇，以生成α，β-不饱和甲基酮，随后通过简单的溶剂将Meerwein-Ponndorf-Verley还原为羰基从丙酮换成异丙醇。此外，Hf-MOF-808饰有钯颗粒，所得材料可用于一锅羟醛缩合反应和随后的高选择性双键还原反应。通过从丙酮到异丙醇的简单溶剂交换，β-不饱和甲基酮和随后的Meerwein-Ponndorf-Verley还原羰基。此外，Hf-MOF-808饰有钯颗粒，所得材料可用于一锅羟醛缩合反应和随后的高选择性双键还原反应。通过从丙酮到异丙醇的简单溶剂交换，β-不饱和甲基酮和随后的Meerwein-Ponndorf-Verley还原羰基。此外，Hf-MOF-808饰有钯颗粒，所得材料可用于一锅羟醛缩合反应和随后的高选择性双键还原反应。

更新日期：2018-07-02

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