CAJ | 학술논문

采用密度泛函B3LYP方法研究了1,2-环丙烷乙酰化糖在氘代氯仿溶液中的水解反应的详细机理。计算结果表明,当H2 O分子从不同方向进攻1,2-环丙烷乙酰化糖分子时,会形成不同的反应途径,当H2 O从糖分子的六元环平面下方进攻时,反应为一步反应,环丙烷的开环步骤为反应决速步,生成α构型产物。当H2 O从糖分子的六元环平面上方进攻时,反应为两步反应,形成产物的氢迁移步骤为决速步,生成β构型产物。 H2 O从糖分子平面下方进攻的反应途径在热力学及动力学上都更有优势,1,2-环丙烷乙酰化糖的水解反应更有利于生成α构型产物,计算结果与实验结果一致。
채용밀도범함B3LYP방법연구료1,2-배병완을선화당재도대록방용액중적수해반응적상세궤리。계산결과표명,당H2 O분자종불동방향진공1,2-배병완을선화당분자시,회형성불동적반응도경,당H2 O종당분자적륙원배평면하방진공시,반응위일보반응,배병완적개배보취위반응결속보,생성α구형산물。당H2 O종당분자적륙원배평면상방진공시,반응위량보반응,형성산물적경천이보취위결속보,생성β구형산물。 H2 O종당분자평면하방진공적반응도경재열역학급동역학상도경유우세,1,2-배병완을선화당적수해반응경유리우생성α구형산물,계산결과여실험결과일치。
The mechanism of the hydrolysis of 1,2-cyclopropaneacetylated sugar in CDCl3 was investigated in detail using the B3LYP method. The computational results indicated that H2 O could attack 1,2-cyclopropaneacetylated sugar from two directions, therefore two paths are obtained. When H2 O attacks the three-membered ring of the cyclopropane from below the surface of the six-membered ring of the sugar( path A) ,the reaction is one-step reaction and the α-configuration product is obtained. The step of the cyclopropane ring opening on the sugar is the rate-determining step(RDS). When H2O attacks the three-membered ring of the cy-clopropane from above the surface of the six-membered ring of the sugar( path B) ,the reaction is composed of two steps and theβ-configuration product is obtained. The hydrogen migration step is the RDS. Path A is predicted to be more kinetically and thermody-namically favored in CDCl3 than path B. The major product is in α-configuration and the results are in agreement with the experi-mental observations.