Deoxydehydration of polyols catalyzed by a molybdenum dioxo-complex supported by a dianionic ONO pincer ligand
Deoxydehydration of polyols catalyzed by a molybdenum dioxo-complex supported by a dianionic ONO pincer ligand
复制标题
双阴离子ONO钳配体支持的钼二氧配合物催化多元醇脱氧脱水
DOI：
10.1039/c9dt03759d
复制
发表时间：
2019
影响因子：
4
通讯作者：
Kilyanek, Stefan M.
中科院分区：
文献类型：
--
作者：
Tran, Randy;Kilyanek, Stefan M.
脱氧脱水(DODH)是将二元醇和多元醇净还原为烯烃或二烯和水。合成了顺式二氧钼双酚ONO络合物，并研究了其对DODH的催化活性。在150-190℃范围内对催化剂进行了活性筛选，得到了高达59%的产率。筛选出PPh3、Na2SO3、锌、碳、3-辛醇和异丙醇为还原剂。此外，还对多种二元醇的反应活性进行了筛选。以(R，R)-(+)-氢化安息香为底物，DODH发生的机理是钼催化剂的还原是二醇氧化生成两个当量醛的结果。这些反应导致反式二苯乙烯和苯甲醛的完全转化率和接近定量的产率。
Deoxydehydration (DODH) is the net reduction of diols and polyols to alkenes or dienes and water. Molybdenum cis-dioxo bis-phenolate ONO complexes were synthesized and have been shown to be active for DODH. Catalysts were screened for activity at 150–190 °C, and appreciable yields of up to 59% were obtained. PPh3, Na2SO3, Zn, C, 3-octanol and 2-propanol were screened as reductants. Additionally, the reactivities of a variety of diols were screened. With (R,R)-(+)-hydrobenzoin as substrate, DODH occurs via a mechanism where reduction of the Mo catalyst is a result of diol oxidation to form two equivalents of aldehyde. These reactions result in complete conversion and near quantitative yields of trans-stilbene and benzaldehyde.