(R)-(E)-1-<(tert-Butyldimethylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-methylhex-3-ene | 138436-23-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R)-(E)-1-<(tert-Butyldimethylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-methylhex-3-ene
• 英文别名: (R)-(E)-1-[(tert-Butyldimethylsilyl)oxy]-2-({[(p-methoxybenzyl)oxy]methoxy}methyl)-5-methylhex-3-ene；tert-butyl-[(E,2R)-2-[(4-methoxyphenyl)methoxymethoxymethyl]-5-methylhex-3-enoxy]-dimethylsilane
• CAS: 138436-23-4
• 化学式: C₂₃H₄₀O₄Si
• 分子量: 408.654
• InChiKey: QEIXKIGXMVXGAY-LCCNJJIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.04
• 重原子数：
  28
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-(E)-1-<(tert-Butyldimethylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-methylhex-3-ene 在 platinum(IV) oxide 、 sodium tetrahydroborate 、 正丁基锂 、 草酰氯 、 9-borabicyclononane 、 氨 、 氢气 、 双氧水 、 4-甲基苯磺酸吡啶 、 lithium 、 碳酸氢钠 、 苯甲酰氯 、 臭氧 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 magnesium bromide 作用下， 以 二氯甲烷 、 叔丁醇 、 苯 为溶剂， 生成 <4R-(4α,4(R*),5β)>-5-<<<(1,1-dimethylethyl)dimethylsilyl>oxy>methyl>-β-methyl-2,2-dimethyl-1,3-dioxane-4-heptanol
  参考文献：
  名称：

  从3-羟基-2-甲基丙酸甲酯和不对称的双（羟甲基）乙醛（BHYMA *）开始，合成降胆固醇药1233A的关键中间体

  摘要：

  化合物2是降胆固醇药1233A 1的总合成的已知中间体，已通过收敛方法以3-羟基-2-甲基丙酸酯6和BHYMA * 5为手性结构单元以高收率合成了化合物2 。

  DOI：

  10.1016/s0040-4039(00)73162-5
• 作为产物：
  描述：

  (E)-2-(3-methyl-1-buten-1-yl)-1,3-propanediol 在 吡啶 、 咪唑 、 氢氧化钾 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 水 、 异丙醇 为溶剂， 反应 11.5h， 生成 (R)-(E)-1-<(tert-Butyldimethylsilyl)oxy>-2-<<<(p-methoxybenzyl)oxy>methoxy>methyl>-5-methylhex-3-ene
  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

• Chemoenzymatic preparation of a key intermediate for carbapenem synthesis starting from asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*)
  作者：Luca Banfi、Giuseppe Guanti、Enrica Narisano

  DOI：10.1016/s0040-4020(01)87214-8

  日期：1993.8

  4-Unsubstituted 2-azetidinones 3a,b, which are useful intermediates for the synthesis of carbapenem antibiotics, have been enantiospecifically and diastereoselectively prepared starting from asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*)4, a new chiral building block obtained through biological methods. The key steps are the highly diastereoselective addition of Me2CuLi to 4 (diast. ratio = 95

  从合成的不对称双（羟甲基）乙醛（BHYMA *）4对映体和非对映选择性地制备了4-非取代的2-氮杂环丁酮3a，b，它们是合成碳青霉烯抗生素的有用中间体，是一种通过生物方法获得的新手性结构单元。关键步骤是将Me 2 CuLi高度非对映选择性地添加到4中（最小比率= 95：5），以及在存在（t Pr）3 Si醚的情况下，通过使用a进行t BuMe 2 Si醚的区域选择性解封闭。新颖的方法。
• Protecting group controlled diastereoselective allylation of asymmetrized bis (hydroxymethyl)acetaldehydes (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/0040-4039(91)80449-g

  日期：1991.11

  MgBr2 catalysed allylation of a series of diprotected asymmetrized bis (hydroxymethyl)acetaldehydes 2 with allyltributylstannane proceeds with good diastereoselectivity. The stereochemical results are in line with a cyclic chelated transition state, where only one of the two CH2OR appendages, due to the different nature of protecting groups, is capable of coordinating the Lewis acid.
• Convergent synthesis of a key intermediate for hypocholesterolemic agent 1233A, starting from methyl 3-hydroxy-2-methylpropanoate and asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*)
  作者：Giuseppe Guanti、Luca Banfi、Giovanna Schmid

  DOI：10.1016/s0040-4039(00)73162-5

  日期：1994.6

  Compound 2, which is a known intermediate for the total synthesis of hypocholesterolemic agent 1233A 1, has been synthesized in good overall yield through a convergent approach, employing 3-hydroxy-2-methylpropanoate 6 and BHYMA* 5 as chiral building blocks.

  化合物2是降胆固醇药1233A 1的总合成的已知中间体，已通过收敛方法以3-羟基-2-甲基丙酸酯6和BHYMA * 5为手性结构单元以高收率合成了化合物2 。
• Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1021/jo00031a039

  日期：1992.2

  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.