1-tetraloyl isobutylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 1-tetraloyl isobutylate
• 英文别名: (1S)-1,2,3,4-tetrahydronaphthalen-1-yl 2-methylpropanoate；[(1S)-1,2,3,4-tetrahydronaphthalen-1-yl] 2-methylpropanoate
• 化学式: C₁₄H₁₈O₂
• 分子量: 218.296
• InChiKey: DZNKOFHXUWTCMG-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-tetraloyl isobutylate 在 sodium hydroxide 作用下， 生成 (S)-(+)-1,2,3,4-四氢-1-萘酚
  参考文献：
  名称：

  Asymmetric Acylation of sec-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center

  摘要：

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.

  DOI：

  10.1021/jo990892p
• 作为产物：
  描述：

  4-nitrophenyl isobutyrate 、 1,2,3,4-四氢-1-萘酚 在 (C5Ph5)Ru(Cl)(CO)2 、 (2S,3R)-3,4-二氢-3-异丙基-2-苯基-2H-嘧啶并[2,1-b]苯并噻唑 、 potassium tert-butylate 、 potassium carbonate 作用下， 反应 72.0h， 以12%的产率得到
  参考文献：
  名称：

  仲醇的酰基动力学动力学拆分：HyperBTM和贝克勒钌络合物的串联催化

  摘要：

  据报道，使用异硫脲衍生的HyperBTM催化剂，通过对映选择性酰化作用，仲醇的非酶动力学动力学拆分（DKR），以及由Bäckvall钌络合物使缓慢反应的醇外消旋化。DKR方法具有高对映选择性（高达99：1），采用易于处理的结晶异丁酸4-硝基苯基酯作为酰化剂，可在室温和环境气氛下进行。通过DFT计算，详细阐述了以阳离子化的HyperBTM催化剂与醇芳基亚基的π电子之间的阳离子-π系统相互作用为特征的立体诱导模型。

  DOI：

  10.1021/acs.joc.1c00545

文献信息

• Acylative Dynamic Kinetic Resolution of Secondary Alcohols: Tandem Catalysis by HyperBTM and Bäckvall’s Ruthenium Complex
  作者：Artis Kinens、Simonas Balkaitis、Omar K. Ahmad、David W. Piotrowski、Edgars Suna

  DOI：10.1021/acs.joc.1c00545

  日期：2021.5.21

  Non-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols by enantioselective acylation using an isothiourea-derived HyperBTM catalyst and racemization of slowly reacting alcohol by Bäckvall’s ruthenium complex is reported. The DKR approach features high enantioselectivities (up to 99:1), employs easy-to-handle crystalline 4-nitrophenyl isobutyrate as the acylating reagent, and proceeds

  据报道，使用异硫脲衍生的HyperBTM催化剂，通过对映选择性酰化作用，仲醇的非酶动力学动力学拆分（DKR），以及由Bäckvall钌络合物使缓慢反应的醇外消旋化。DKR方法具有高对映选择性（高达99：1），采用易于处理的结晶异丁酸4-硝基苯基酯作为酰化剂，可在室温和环境气氛下进行。通过DFT计算，详细阐述了以阳离子化的HyperBTM催化剂与醇芳基亚基的π电子之间的阳离子-π系统相互作用为特征的立体诱导模型。
• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.