(3S,4S,5R)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate | 138768-09-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (3S,4S,5R)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate
• 英文别名: tert-butyl (3S)-3-[(2S,3R)-3-[[tert-butyl(diphenyl)silyl]oxymethyl]oxiran-2-yl]-3-hydroxypropanoate
• CAS: 138768-09-9
• 化学式: C₂₆H₃₆O₅Si
• 分子量: 456.654
• InChiKey: GNFZGMMRJDDYAS-ZDXQCDESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,4S,5R)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以97%的产率得到(4S,5S)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-1-hydroxy-ethyl]-4-hydroxy-dihydro-furan-2-one
  参考文献：
  名称：

  取代的β-羟基γ-丁内酯和2-脱氧己呋喃糖苷的短合成

  摘要：

  通过非对映选择性醛缩甜菜碱酯烯酸酯和旋光性α，β-环氧醛获得的γ，δ-环氧β-羟基雌二醇进行定量立体控制的内酯化，然后还原生成2-脱氧六呋喃糖苷。

  DOI：

  10.1016/s0040-4039(00)91641-1
• 作为产物：
  描述：

  (Z)-4-((tert-butyldiphenylsilyl)oxy)but-2-en-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 D-(-)-酒石酸二异丙酯 、 3 A molecular sieve 、 三氧化硫吡啶 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 36.75h， 生成 (3S,4S,5R)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate
  参考文献：
  名称：

  除烯醇锂之外的手性α，β-环氧醛的非对映体分化

  摘要：

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。

  DOI：

  10.1016/s0040-4020(01)82375-9

文献信息

• Diastereoselection in the addition of enolates to chiral α,β-epoxyaldehydes
  作者：Jean-Marc Escudier、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4039(00)92381-5

  日期：1991.9

  The stereochemistry of addition of lithium enolates to the α,β-epoxyaldehydes 1z–3 has been investigated. Moderate to high diastereoselectivity (up to 13:1) is obtained in favour of the anti isomer, which is explained by the Felkin-Anh model for asymmetric induction.

  已经研究了在α，β-环氧醛1z – 3中添加烯醇锂的立体化学。获得中等至高的非对映选择性（高达13：1），有利于抗异构体，这由非对称诱导的Felkin-Anh模型解释。
• Diastereoselectivity in theLewis acid mediated aldol reaction of chiral α, β-epoxyaldehydes with a ketene silyl acetal
  作者：E. Fontaine、M. Baltas、J. -M. Escudier、L. Gorrichon

  DOI：10.1007/bf00807077

  日期：1996.5

  The Lewis acid mediated aldol reaction of chiral alpha, beta-cis and trans epoxyaldehydes 1 and 2 with tert-butyl ketene silyl acetal proceeds mainly with anti diastereofacial preference. The best results were obtained for cis epoxyaldehyde 1 in the presence of catalytic amounts of BiCl3 . 1.5 eq. ZnI2 (anti:syn similar to 13:1), whereas the poorest stereoselectivity was observed when an excess of LiClO4 was used (anti:syn similar to 1:1) The more stable epoxyaldehyde conformers were determined and the diastereofacial preference was found to be in agreement with a nucleophilic attack on the energetically more favoured conformers.
• Mukaiyama aldolisation reactions of α,β-epoxyaldehydes in aqueous media
  作者：Yvan Ruland、Pierre Noereuil、Michel Baltas

  DOI：10.1016/j.tet.2005.07.027

  日期：2005.9

  The Mukaiyama aldolisation reaction in aqueous media of cis and trans alpha,beta-epoxyaldehydes with tert-butyldimethylsilyl ketene acetal in the presence of Lewis's acids was studied. Sc(OTf)(3) gave the best results in terms of selectivity. The same reaction of cis and trans alpha., beta-epoxyaldehydes with the enoxysilane of ethyl pyruvate resulted in epoxy Substituted ulosonic derivatives issued from a double sequential condensation of the pyruvate on the epoxy derivatives. (c) 2005 Elsevier Ltd. All rights reserved.
• Diastereoface differentiation in addition of lithium enolates to chiral α,β-epoxyaldehydes
  作者：Jean-Marc Escudier、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4020(01)82375-9

  日期：1993.6

  aldolisation reaction of lithium ester enolates with chiral α,β-epoxyaldehydes 2a–2f has been investigated. The reaction proceeds with diastereofacial preference in favour of the anti isomer (anti:syn ≈ 4:1) and can be greatly enhanced in the case of cis α,β-epoxy-aldehydes 2a–2c by a synergic effect of temperature and enolate excess (anti:syn 13:1). The Felkin-Ahn model can explain the results obtained

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。
• A short synthesis of substituted β-hydroxy γ-butyrolactones and 2-deoxyhexofuranosides
  作者：Jean-Marc Escudier、Michel Baltas、Gorrichon Liliane

  DOI：10.1016/s0040-4039(00)91641-1

  日期：1992.3

  The γ,δ-epoxy β-hydroxyestes obtained by diastereoselective aldolisation beetwen ester enolates and optically active α,β-epoxyaldehydes, undergo quantitative stereocontrolled lactonisation which can be followed by reduction to provide 2-deoxy hexofuranosides.

  通过非对映选择性醛缩甜菜碱酯烯酸酯和旋光性α，β-环氧醛获得的γ，δ-环氧β-羟基雌二醇进行定量立体控制的内酯化，然后还原生成2-脱氧六呋喃糖苷。