A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with...A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with n butyl lithium. Mandelonitrile was prepared in an isolated yield 70% with more than \{e.e.\} =60%. The effect of solvents and the amount of catalyst on enantioselectivity was also investigated.展开更多
Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with （R）-oxynitrilase from defatted Prunus Japonica seed meal for the prep...Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with （R）-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active （R）-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess （e.e.）. Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% （by volume）, 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for （R）-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.展开更多
文摘A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with n butyl lithium. Mandelonitrile was prepared in an isolated yield 70% with more than \{e.e.\} =60%. The effect of solvents and the amount of catalyst on enantioselectivity was also investigated.
文摘Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with （R）-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active （R）-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time. For better understanding of the reaction, various influential variables were examined with respect to the initial reaction rate, the substrate conversion and the product enantiomeric excess （e.e.）. Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested. The optimal concentrations of Prunus Japonica seed meal powder, acetyltrimethylsilane and acetone cyanohydrin, volume ratio of aqueous phase to organic phase, buffer pH value and the reaction temperature were 34.5g·L^-1 and 14mmol· L^-1, 28mmol· L^-1, 13% （by volume）, 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34 mmol·L^-1·h^-1, 99.0% and 99.0%, respectively. The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for （R）-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone.
