(3R,4S,5S)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate | 153321-79-0

• 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: (3R,4S,5S)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate
• 英文别名: tert-butyl (3R)-3-[(2S,3S)-3-[[tert-butyl(diphenyl)silyl]oxymethyl]oxiran-2-yl]-3-hydroxypropanoate
• CAS: 153321-79-0
• 化学式: C₂₆H₃₆O₅Si
• 分子量: 456.654
• InChiKey: GNFZGMMRJDDYAS-GPXNEJASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  32.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.29
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  叔丁基二甲基氯硅烷 、 (3R,4S,5S)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate 在 咪唑 、 4-二甲氨基吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以60%的产率得到(R)-3-(tert-Butyl-dimethyl-silanyloxy)-3-[(2R,3S)-3-(tert-butyl-diphenyl-silanyloxymethyl)-oxiranyl]-propionic acid tert-butyl ester
  参考文献：
  名称：

  Diastereoselectivity in theLewis acid mediated aldol reaction of chiral α, β-epoxyaldehydes with a ketene silyl acetal

  摘要：

  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.

  DOI：

  10.1007/bf00807077
• 作为产物：
  描述：

  醋酸叔丁酯 在 六甲基磷酰三胺 、 bismuth(III) chloride 、 zinc(II) iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 Petroleum ether 为溶剂， 反应 12.58h， 生成 (3R,4S,5S)-tert-butyl <6-(tert-butyldiphenylsilyloxy)-4,5-epoxy-3-hydroxy>hexanoate
  参考文献：
  名称：

  Diastereoselectivity in theLewis acid mediated aldol reaction of chiral α, β-epoxyaldehydes with a ketene silyl acetal

  摘要：

  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.

  DOI：

  10.1007/bf00807077

文献信息

• 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。
• 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.