The Strecker reaction was performed via a one-pot three component condensation of hetero aromatic/ aromatic aldehydes, secondary amines and trimetylsilyl cyanide in the presence of propylphosphonic anhydride （T3P） t...The Strecker reaction was performed via a one-pot three component condensation of hetero aromatic/ aromatic aldehydes, secondary amines and trimetylsilyl cyanide in the presence of propylphosphonic anhydride （T3P） to accomplish the corresponding α-aminonitriles. The main advantages of this method are very short reaction time and excellent yields.展开更多
Introduction α-Aminonitrile(or aminoacetonitrile) is a kind of reactive bioorganic molecules, and it may exist in insterstellar clouds. its importance lies in that a-aminonitrile may play a role in the generation of ...Introduction α-Aminonitrile(or aminoacetonitrile) is a kind of reactive bioorganic molecules, and it may exist in insterstellar clouds. its importance lies in that a-aminonitrile may play a role in the generation of large carbon-nitrogen chain molecules. By means of flash vacuum thermolysis and gas-solid reaction (FVT-GSR) tech-nique, Guillemin, et al., studied the thermolysis of a-aminonitrile, they considered that the elimination of HCN (shown as following) is a key step in many reactions of α-展开更多
Silica-bonded N-propyl diethylenetriamine sulfamic acid (SBPDSA) is employed as a recyclable catalyst to synthesize α-aminonitriles. These syntheses involved one-pot condensation of an aldehyde, an amine, and trimeth...Silica-bonded N-propyl diethylenetriamine sulfamic acid (SBPDSA) is employed as a recyclable catalyst to synthesize α-aminonitriles. These syntheses involved one-pot condensation of an aldehyde, an amine, and trimethylsilyl cyanide under mild reaction conditions at room temperature. SBPDSA was recycled seven times in the condensation of benzaldehyde, aniline, and trimethylsilyl cyanide without reduction of its catalytic activity.展开更多
We report a highly enantioselective one-pot facile synthesis of fluorinated Cα-tetrasubstituted amino nitriles from α-fluoroalkyl α-aryl keo tones, anilines, and TMSCN through a sequential p-TsOH catalyzed ketimine...We report a highly enantioselective one-pot facile synthesis of fluorinated Cα-tetrasubstituted amino nitriles from α-fluoroalkyl α-aryl keo tones, anilines, and TMSCN through a sequential p-TsOH catalyzed ketimine formation and chiral bifunctional tertiary amine mediated asymmetric Strecker reaction. This one-pot approach has two important advantages. First, it greatly improves the overall yield of the synthesis of chiral Cα-tetrasubstituted fluorinated aminonitriles from ketones, because the purification of a-fluorinated ketimines by column chromatography suffers from great yield loss. Second, it represents the first example of asymmetric tandem reactions that can simultaneously reuse the by-product and catalyst from the upstream step as a promoter and an additive to improve the reactivity and enantioselectivity of the subsequent catalytic enantioselective reaction, respectively. It could utilize the by-product H_2O generated in-situ from the ketimine formation step to activate TMSCN to form HCN, and concurrently reuse the remaining p-TsOH acid as an additive to improve enantioselectivity.展开更多
基金the Board of Research in Nuclear Sciences (BRNS),Mumbai,India for providing the financial support (No.2012/37C/33/BRNS)
文摘The Strecker reaction was performed via a one-pot three component condensation of hetero aromatic/ aromatic aldehydes, secondary amines and trimetylsilyl cyanide in the presence of propylphosphonic anhydride （T3P） to accomplish the corresponding α-aminonitriles. The main advantages of this method are very short reaction time and excellent yields.
基金Supported by the National Natural Science Foundation of China Jiangxi Province.
文摘Introduction α-Aminonitrile(or aminoacetonitrile) is a kind of reactive bioorganic molecules, and it may exist in insterstellar clouds. its importance lies in that a-aminonitrile may play a role in the generation of large carbon-nitrogen chain molecules. By means of flash vacuum thermolysis and gas-solid reaction (FVT-GSR) tech-nique, Guillemin, et al., studied the thermolysis of a-aminonitrile, they considered that the elimination of HCN (shown as following) is a key step in many reactions of α-
文摘Silica-bonded N-propyl diethylenetriamine sulfamic acid (SBPDSA) is employed as a recyclable catalyst to synthesize α-aminonitriles. These syntheses involved one-pot condensation of an aldehyde, an amine, and trimethylsilyl cyanide under mild reaction conditions at room temperature. SBPDSA was recycled seven times in the condensation of benzaldehyde, aniline, and trimethylsilyl cyanide without reduction of its catalytic activity.
基金We thank the financial support from the National Natural Science Foundation of China （Nos. 21472049, 21725203）.
文摘We report a highly enantioselective one-pot facile synthesis of fluorinated Cα-tetrasubstituted amino nitriles from α-fluoroalkyl α-aryl keo tones, anilines, and TMSCN through a sequential p-TsOH catalyzed ketimine formation and chiral bifunctional tertiary amine mediated asymmetric Strecker reaction. This one-pot approach has two important advantages. First, it greatly improves the overall yield of the synthesis of chiral Cα-tetrasubstituted fluorinated aminonitriles from ketones, because the purification of a-fluorinated ketimines by column chromatography suffers from great yield loss. Second, it represents the first example of asymmetric tandem reactions that can simultaneously reuse the by-product and catalyst from the upstream step as a promoter and an additive to improve the reactivity and enantioselectivity of the subsequent catalytic enantioselective reaction, respectively. It could utilize the by-product H_2O generated in-situ from the ketimine formation step to activate TMSCN to form HCN, and concurrently reuse the remaining p-TsOH acid as an additive to improve enantioselectivity.
