1,4,10,10-tetramethyl-3-oxo-5-aza-4-boratricyclo[5.2.1.0.2,6]decane | 161343-80-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,4,10,10-tetramethyl-3-oxo-5-aza-4-boratricyclo[5.2.1.0.2,6]decane
• CAS: 161343-80-2
• 化学式: C₁₁H₂₀BNO
• 分子量: 193.097
• InChiKey: HCCZMBSXUFLKLX-FTYOSLGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.26
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  三甲基环三硼氧烷 、 cis-endo-3-aminoisoborneol 以 甲苯 为溶剂， 以91%的产率得到1,4,10,10-tetramethyl-3-oxo-5-aza-4-boratricyclo[5.2.1.0.2,6]decane
  参考文献：
  名称：

  A combined synthetic and ab initio study of chiral oxazaborolidines structure and enantioselectivity relationships

  摘要：

  Investigations into the relationship of oxazaborolidine structure to the enantioselectivity obtained in the reduction of prochiral ketones revealed the intrinsic power of the molecular recognition element in the catalytic reduction. This molecular recognition, two-point binding of borane and the ketonic oxygen atom by the oxazaborotidine, assembles a trimolecular complex which provides high enantiomeric excess. Enantiomeric excess was demonstrated to be dependent on the extent to which one oxazaborolidine face was precluded from attaining two-point binding and on nonbonded interactions that developed during formation of the borane-oxazaborolidine complex. As a result, erythro-substituted oxazaborolidines were demonstrated to be useful catalysts for enantioselective reduction of prochiral ketones. Ab initio molecular orbital calculations have been used to locate possible complexes and transition state assemblies that correspond to catalyst-borane and the trimolecular complex on a proposed reduction pathway. Geometry optimizations were carried out at the 3-21G, 6-31G(d), and MP2/6-31G(d) levels of theory. Correlation energies were computed via Moller-Plesset perturbation theory to the second order (MP2). Relative activation energies establish correctly the observed enantioselectivity of the two best oxazaborolidine catalysts in this study. Additionally, the diminished enantioselectivity of N-methyl-substituted catalysts was traced to conformational changes in the exo transition state. Though the relative energies obtained from the various levels of theory are similar, absolute complexation and activation energies are found to vary considerably with the level of theory employed. The existence of key intermediates was found to depend on the level of theory.

  DOI：

  10.1021/ja00098a012