The direct catalytic oxidation of alcohols to esters is very appealing,but the economical-friendly catalysis systems are not yet well established.Herein,we show that a pure inorganic ligand-supported single-atomic cob...The direct catalytic oxidation of alcohols to esters is very appealing,but the economical-friendly catalysis systems are not yet well established.Herein,we show that a pure inorganic ligand-supported single-atomic cobalt compound,(NH_(4))_(3)[CoMo_(6)O_(18)(OH)_(6)](simplified as CoMo_(6)),could be used as a heterogeneous catalyst and effectively promote this type of reaction in the presence of 30%H_(2)O_(2)using KCl as an additive.The oxidative cross-esterification of various alcohols(aromatic and aliphatic)could be achieved under mild conditions in nearly all cases,affording the corresponding esters in high yields,including several drug molecules and natural products.Detailed studies have revealed that chloride ion is able to bind to the CoMo_(6)to form a supramolecular dimer 2(CoMo_(6)∙Cl),which can effectively catalyze the reaction via a synergistic effect from chloride ion and CoMo_(6).Mechanism studies and control reactions demonstrate that the esterification proceeds via the key oxidative immediate of aldehydes.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.21971134,21225103,21871183,and 21901038)Shanghai Natural Science Foundation of China(No.18ZR1437900)+2 种基金Tsinghua University Initiative Foundation Research Program(No.20131089204)the State Key Laboratory of Natural and Biomimetic Drugs(K20160202)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.The Starting fund for high-level talents of Donghua University is also gratefully acknowledged.
文摘The direct catalytic oxidation of alcohols to esters is very appealing,but the economical-friendly catalysis systems are not yet well established.Herein,we show that a pure inorganic ligand-supported single-atomic cobalt compound,(NH_(4))_(3)[CoMo_(6)O_(18)(OH)_(6)](simplified as CoMo_(6)),could be used as a heterogeneous catalyst and effectively promote this type of reaction in the presence of 30%H_(2)O_(2)using KCl as an additive.The oxidative cross-esterification of various alcohols(aromatic and aliphatic)could be achieved under mild conditions in nearly all cases,affording the corresponding esters in high yields,including several drug molecules and natural products.Detailed studies have revealed that chloride ion is able to bind to the CoMo_(6)to form a supramolecular dimer 2(CoMo_(6)∙Cl),which can effectively catalyze the reaction via a synergistic effect from chloride ion and CoMo_(6).Mechanism studies and control reactions demonstrate that the esterification proceeds via the key oxidative immediate of aldehydes.
