(S)-(E)-2-<<(Benzyloxy)methoxy>methyl>-1-<<(tert-butyldiphenylsilyl)oxy>methyl>non-3-en | 138513-57-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (S)-(E)-2-<<(Benzyloxy)methoxy>methyl>-1-<<(tert-butyldiphenylsilyl)oxy>methyl>non-3-en
• 英文别名: tert-butyl-diphenyl-[(E,2S)-2-(phenylmethoxymethoxymethyl)non-3-enoxy]silane
• CAS: 138513-57-2
• 化学式: C₃₄H₄₆O₃Si
• 分子量: 530.823
• InChiKey: YETLWWZYIUKVGX-WZYCLFSOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.51
• 重原子数：
  38.0
• 可旋转键数：
  16.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-(E)-2-<<(Benzyloxy)methoxy>methyl>-1-<<(tert-butyldiphenylsilyl)oxy>methyl>non-3-en 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 以60%的产率得到(S)-2-<<(Benzyloxy)methoxy>methoxy>-3-<(tert-butyldiphenylsilyl)oxy>-1-propanol
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039
• 作为产物：
  描述：

  Acetic acid (E)-(R)-2-hydroxymethyl-non-3-enyl ester 在 氢氧化钾 、 N,N-二异丙基乙胺 作用下， 生成 (S)-(E)-2-<<(Benzyloxy)methoxy>methyl>-1-<<(tert-butyldiphenylsilyl)oxy>methyl>non-3-en
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039

文献信息

• Enzymes as selective reagents in organic synthesis: Enantioselective preparation of “asymmetrized tris (hydroxymethyl)methane”
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/s0040-4039(00)99101-9

  日期：1989.1

  A new C-4 chiral building block, that is a tris (hydroxymethyl)methane derivative where the three equivalent hydroxymethyl groups have been differentiated [(THYM)*], was prepared with excellent enantioselection, through PPL catalysed monohydrolysis of prochiral diacetate 3.

  通过PPL催化前手性双乙酸3的单水解，制备了具有优异对映异构性的新的C-4手性结构单元，该结构是三（羟甲基）甲烷衍生物，其中三个等效的羟甲基已被区分[（THYM）* ] 。
• GUANTI, GIUSEPPE;BANFI, LUCA;NARISANO, ENRICA, TETRAHEDRON LETT., 30,(1989) N0, C. 2697-2698
  作者：GUANTI, GIUSEPPE、BANFI, LUCA、NARISANO, ENRICA

  DOI：——

  日期：——