Numerical simulation of transient mass transfer to a single dropcontrolled by the internal resistance or by the resistance in bothphases was mathematically formulated and simulated in aboundary-fitted orthogonal coord...Numerical simulation of transient mass transfer to a single dropcontrolled by the internal resistance or by the resistance in bothphases was mathematically formulated and simulated in aboundary-fitted orthogonal coordinate system. The simulated resultson the transient mass transfer dominated by the internal resistanceare in good agreement with the Newman and Kronig-Brink models fordrops with low Reynolds number. When the drop Reynolds number is upto 200, the mass transfer coefficient from numerical simulation isvery low as compared with The Handlos-Baron model.展开更多
Allylic amines and 1,3-oxazinanes are valuable molecular skeletons in organic synthesis and pharmaceutical industry.A straightforward way to such two types of compounds by solvent-controlled rare-earth metal Lewis aci...Allylic amines and 1,3-oxazinanes are valuable molecular skeletons in organic synthesis and pharmaceutical industry.A straightforward way to such two types of compounds by solvent-controlled rare-earth metal Lewis acid-catalyzed transformations of 2-(hetero)aryl-N-sulfonylazetidines:the ring-opening isomerization of azetidines to allylic amines and the annulation of azetidines with aldehydes to 1,3-oxazinanes are reported.These two reactions feature scalability,low catalyst loading,mild reaction conditions,excellent yields and regioselectivity with demonstrated utility in three-step product transformations to naftifine,abamine and abamine SG.展开更多
Stereochemical control is an important issue in carbohydrate synthesis.Glycosyl donors with participating acyl protective groups on 2-O have been shown to give 1,2-trans glycosides reliably under the pre-activation ba...Stereochemical control is an important issue in carbohydrate synthesis.Glycosyl donors with participating acyl protective groups on 2-O have been shown to give 1,2-trans glycosides reliably under the pre-activation based reaction condition.In this work,the effects of additives and reaction solvents on stereoselectivity were examined using donors without participating protective groups on 2-O.While several triflate salt additives did not have major effects,the amount of AgOTf was found to significantly impact the reaction outcome.Excess AgOTf led to lower stereochemical control presumably due to its coordination with the glycosyl triflate intermediate and a more SN1 like reaction pathway.In contrast,the stereoselectivity could be directed by reaction solvents,with diethyl ether favoring the formation of glycosides and dichloromethane leading to β isomers.The trend of stereochemical dependence on reaction solvent was applicable to a variety of building blocks including the selective formation of β-mannosides.展开更多
基金Supported by the National Natural Science Foundation of China (No. 29792074, No. 29836130} and SINOPEC.
文摘Numerical simulation of transient mass transfer to a single dropcontrolled by the internal resistance or by the resistance in bothphases was mathematically formulated and simulated in aboundary-fitted orthogonal coordinate system. The simulated resultson the transient mass transfer dominated by the internal resistanceare in good agreement with the Newman and Kronig-Brink models fordrops with low Reynolds number. When the drop Reynolds number is upto 200, the mass transfer coefficient from numerical simulation isvery low as compared with The Handlos-Baron model.
文摘Allylic amines and 1,3-oxazinanes are valuable molecular skeletons in organic synthesis and pharmaceutical industry.A straightforward way to such two types of compounds by solvent-controlled rare-earth metal Lewis acid-catalyzed transformations of 2-(hetero)aryl-N-sulfonylazetidines:the ring-opening isomerization of azetidines to allylic amines and the annulation of azetidines with aldehydes to 1,3-oxazinanes are reported.These two reactions feature scalability,low catalyst loading,mild reaction conditions,excellent yields and regioselectivity with demonstrated utility in three-step product transformations to naftifine,abamine and abamine SG.
基金the National Institutes of Health (R01-GM-72667) for financial support of this work
文摘Stereochemical control is an important issue in carbohydrate synthesis.Glycosyl donors with participating acyl protective groups on 2-O have been shown to give 1,2-trans glycosides reliably under the pre-activation based reaction condition.In this work,the effects of additives and reaction solvents on stereoselectivity were examined using donors without participating protective groups on 2-O.While several triflate salt additives did not have major effects,the amount of AgOTf was found to significantly impact the reaction outcome.Excess AgOTf led to lower stereochemical control presumably due to its coordination with the glycosyl triflate intermediate and a more SN1 like reaction pathway.In contrast,the stereoselectivity could be directed by reaction solvents,with diethyl ether favoring the formation of glycosides and dichloromethane leading to β isomers.The trend of stereochemical dependence on reaction solvent was applicable to a variety of building blocks including the selective formation of β-mannosides.
