COMPUTATIONAL ELUCIDATION OF THE CATALYTIC MECHANISM FOR KETONE REDUCTION BY AN OXAZABOROLIDINE-BORANE ADDUCT
COMPUTATIONAL ELUCIDATION OF THE CATALYTIC MECHANISM FOR KETONE REDUCTION BY AN OXAZABOROLIDINE-BORANE ADDUCT
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DOI：
10.1039/c39940001651
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发表时间：
1994-07-21
影响因子：
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通讯作者：
WILLIAMS, IH
中科院分区：
文献类型：
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作者：
LINNEY, LP;SELF, CR;WILLIAMS, IH
用AM 1半经验分子轨道计算确定了（S）-脯氨酸→恶唑硼烷→ THF →硼烷→丙酮催化还原反应全循环的反应途径，包括所有过渡结构的表征;用于酮配位的过渡结构的能量几乎与用于速率限制的双转移步骤的能量一样高，计算的THF-[H-2（3）]硼烷还原反应的动力学同位素效应与实验结果雅阁。
The reaction pathway around the complete catalytic cycle for THF-borane reduction of propanone catalysed by the oxazaborolidine from (S)-proline has been determined by AM1 semiempirical MO calculations, including characterisation of all transition structures; the transition structure for ketone coordination is almost as high in energy as that for the rate-limiting hydride-transfer step, and the calculated kinetic isotope effect for reduction by THF-[H-2(3)]borane is in accord with experiment.