(S)-3,3-diethoxypropane-1,2-diol | 139165-65-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-3,3-diethoxypropane-1,2-diol
• 英文别名: l-Glyceraldehyde-diethylacetal；(2S)-3,3-diethoxypropane-1,2-diol
• CAS: 139165-65-4
• 化学式: C₇H₁₆O₄
• 分子量: 164.202
• InChiKey: BPNZBKXZVJVEJD-LURJTMIESA-N

物化性质

• 沸点：
  278.8±35.0 °C(Predicted)
• 密度：
  1.076±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  环氧丙烯醛缩二乙醇 在 epoxide hydrolase from Aspergillus niger, Leu₂₁₅Phe/Ala₂₁₇Asn/Arg₂₁₉Ser/Met₃₂₉Pro/Leu₃₃₀Tyr/Cys₃₅₀Val/Leu₂₄₉Tyr/Thr₃₁₇Trp/Thr₃₁₈Val mutant 、 水 作用下， 以 乙醇 为溶剂， 生成 (S)-3,3-diethoxypropane-1,2-diol 、 (R)-glycidaldehyde diethyl acetal
  参考文献：
  名称：

  Reetz, Manfred T.; Bocola, Marco; Wang, Li-Wen, Journal of the American Chemical Society, 2009, vol. 131, p. 7334 - 7343

  摘要：

  DOI：

文献信息

• Enantioselective silyl protection of alcohols promoted by a combination of chiral and achiral Lewis basic catalysts
  作者：Nathan Manville、Hekla Alite、Fredrik Haeffner、Amir H. Hoveyda、Marc L. Snapper

  DOI：10.1038/nchem.1708

  日期：2013.9

  Catalytic enantioselective monosilylations of diols and polyols furnish valuable alcohol-containing molecules in high enantiomeric purity. These transformations, however, require high catalyst loadings (20–30 mol%) and long reaction times (2–5 days). Here, we report that a counterintuitive strategy involving the use of an achiral co-catalyst structurally similar to the chiral catalyst provides an effective solution to this problem. A combination of seemingly competitive Lewis basic molecules can function in concert such that one serves as an achiral nucleophilic promoter and the other performs as a chiral Brønsted base. On the addition of 7.5–20 mol% of a commercially available N-heterocycle (5-ethylthiotetrazole), reactions typically proceed within one hour, and deliver the desired products in high yields and enantiomeric ratios. In some instances, there is no reaction in the absence of the achiral base, yet the presence of the achiral co-catalyst gives rise to facile formation of products in high enantiomeric purity. A counter-intuitive strategy that combines a chiral Lewis base catalyst with an achiral Lewis base co-catalyst results in an exceptionally large increase in the facility of catalytic enantioselective silylation of polyols. The catalytic ensemble drives such reactions to completion within a few hours, rather than the usual two–five days, without loss of enantioselectivity.

  二元醇和多元醇的催化对映体选择性单硅烷化反应可以提供高对映体纯度的有价值含醇分子。然而，这些转化需要较高的催化剂负载量（20-30 摩尔%）和较长的反应时间（2-5 天）。在此，我们报告了一种反直觉策略，即使用结构上与手性催化剂相似的非手性辅助催化剂，从而有效地解决了这一问题。看似相互竞争的路易斯碱分子组合可以协同发挥作用，其中一个作为非手性亲核促进剂，另一个作为手性布氏碱。加入7.5â20Â mol%的市售N-杂环（5-乙基噻四唑）后，反应通常会在一小时内进行，并以较高的产率和对映体比率得到所需的产物。在某些情况下，如果没有非手性碱，则不会发生反应，但如果有非手性辅助催化剂存在，则很容易形成对映体纯度很高的产物。将手性路易斯碱催化剂与非手性路易斯碱助催化剂结合在一起的反直觉策略可显著提高多元醇的对映选择性硅烷化催化效率。这种催化组合可在几小时内完成此类反应，而不是通常的两天到五天，而且不会丧失对映选择性。
• CATALYTIC ENANTIOSELECTIVE SILYLATIONS OF SUBSTRATES
  申请人：Hoveyda Amir H.

  公开号：US20090312559A1

  公开（公告）日：2009-12-17

  The present invention provides methods, compositions and systems for silylation of substrates, including direct asymmetric silylation of a substrate to provide enantiomerically enriched silylated products.

  本发明提供了用于硅烷化底物的方法、组合物和系统，包括直接不对称硅烷化底物以提供对映选择性富集的硅烷化产物。
• Kinetic Resolution of 1,2-Diols through Highly Site- and Enantioselective Catalytic Silylation
  作者：Yu Zhao、Aurpon W. Mitra、Amir H. Hoveyda、Marc L. Snapper

  DOI：10.1002/anie.200703650

  日期：2007.11.12
• [EN] CATALYTIC ENANTIOSELECTIVE SILYLATIONS OF SUBSTRATES<br/>[FR] SILYLATIONS CATALYTIQUES ENANTIOSELECTIVES DE SUBSTRATS
  申请人：TRUSTEES BOSTON COLLEGE

  公开号：WO2007082026A2

  公开（公告）日：2007-07-19

  [EN] The present invention provides methods, compositions and systems for silylation of substrates, including direct asymmetric silylation of a substrate to provide enantiomerically enriched silylated products.
  [FR] La présente invention concerne des procédés, des compositions et des dispositifs pour la silylation de substrats, y compris la silylation asymétrique directe d'un substrat pour obtenir des produits silylés énantiomériquement enrichis.