O,O'-di(tert-butoxycarbonyl)-1,2-trans-cyclohexanediol

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: O,O'-di(tert-butoxycarbonyl)-1,2-trans-cyclohexanediol
• 英文别名: tert-butyl [(1R,2R)-2-[(2-methylpropan-2-yl)oxycarbonyloxy]cyclohexyl] carbonate
• 化学式: C₁₆H₂₈O₆
• 分子量: 316.395
• InChiKey: BVSDMCDXAAFIHL-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  二碳酸二叔丁酯 、 trans-1,2-cyclohexandiol 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 以78%的产率得到O-(tert-butoxycarbonyl)-1,2-trans-cyclohexanediol
  参考文献：
  名称：

  Lipophilic Oligopeptides for Chemo- and Enantioselective Acyl Transfer Reactions onto Alcohols

  摘要：

  Inspired by the extraordinary selectivities of acylases, we envisioned the use of lipophilic oligopeptidic organocatalysts for the acylative kinetic resolution/desymmetrization of rac- and meso-cycloalkane-1,2-diols. Here we describe in a full account the discovery and development process from the theoretical concept to the final catalyst, including scope and limitations. Competition experiments with various alcohols and electrophiles show the full potential of the employed oligopeptides. Additionally, we utilized NMR and IR-spectroscopic methods as well as computations to shed light on the factors responsible for the selectivity. The catalyst system can be readily modified to a multicatalyst by adding other catalytically active amino acids to the peptide backbone, enabling the stereoselective one-pot synthesis of complex molecules from simple starting materials.

  DOI：

  10.1021/jo401195c

文献信息

• Di-<i>tert</i>-butyl Dicarbonate and 4-(Dimethylamino)pyridine Revisited. Their Reactions with Amines and Alcohols¹
  作者：Yochai Basel、Alfred Hassner

  DOI：10.1021/jo000257f

  日期：2000.10.1

  The reaction of BOC2O in the presence and absence of DMAP was examined with some amines, alcohols, diols, amino alcohols, and aminothiols. Often, unusual products were observed depending on the ratio of reagents, reaction time, polarity of solvent, pK(a) of alcohols, or type of amine (primary or secondary). In reactions of aliphatic alcohols with BOC2O/DMAP, we isolated for the first time carbonic-carbonic anhydride intermediates; this helps explain the formation of symmetrical carbonates in addition to the O-BOC products. In the case of secondary amines, we succeeded to isolate unstable carbamic-carbonic anhydride intermediates that in the presence of DMAP led to the final N-BOC product. The effect of N-methylimidazole in place of DMAP was also examined.
• Lipophilic Oligopeptides for Chemo- and Enantioselective Acyl Transfer Reactions onto Alcohols
  作者：Christian E. Müller、Daniela Zell、Radim Hrdina、Raffael C. Wende、Lukas Wanka、Sören M. M. Schuler、Peter R. Schreiner

  DOI：10.1021/jo401195c

  日期：2013.9.6

  Inspired by the extraordinary selectivities of acylases, we envisioned the use of lipophilic oligopeptidic organocatalysts for the acylative kinetic resolution/desymmetrization of rac- and meso-cycloalkane-1,2-diols. Here we describe in a full account the discovery and development process from the theoretical concept to the final catalyst, including scope and limitations. Competition experiments with various alcohols and electrophiles show the full potential of the employed oligopeptides. Additionally, we utilized NMR and IR-spectroscopic methods as well as computations to shed light on the factors responsible for the selectivity. The catalyst system can be readily modified to a multicatalyst by adding other catalytically active amino acids to the peptide backbone, enabling the stereoselective one-pot synthesis of complex molecules from simple starting materials.