(2S,3S)-3-((tert-butyldimethylsilyloxy)methyl)oxirane-2-carbaldehyde

• 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: (2S,3S)-3-((tert-butyldimethylsilyloxy)methyl)oxirane-2-carbaldehyde
• 英文别名: (-)-(2R,3S)-4-(tert-butyldimethylsilyloxy)-2,3-epoxybutan-1-al；(2S,3S)-3-({[Tert-butyl(dimethyl)silyl]oxy}methyl)-2-oxiranecarbaldehyde；(2S,3S)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]oxirane-2-carbaldehyde
• 化学式: C₁₀H₂₀O₃Si
• 分子量: 216.352
• InChiKey: ZZEAXSVHLYHJBB-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.97
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S)-3-((tert-butyldimethylsilyloxy)methyl)oxirane-2-carbaldehyde 在 sodium azide 、 氯化铵 作用下， 以 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 (4S,5R,E)-ethyl 4-azido-6-(tert-butyldimethylsilyloxy)-5-hydroxyhex-2-enoate
  参考文献：
  名称：

  抗流感药（-）-oseltamivir游离碱和（-）-甲基3- epi- shikimate †的合成

  摘要：

  抗流感药物（-）-oseltamivir游离碱（7.1％的总产率; 98％ee）和3-- Epi- shikimate（-）-甲基-甲基（16％的总产率; 98％ee）的新对映体选择性合成从容易获得的原材料中进行描述。醛的无尖锐不对称环氧化和非对映选择性Barbier烯丙基化是手性结合过程中的关键反应，而环己烯羧酸酯核则是通过闭环易位反应构建的。

  DOI：

  10.1039/c2ob25635e
• 作为产物：
  描述：

  (Z)-4-(tert-butyldimethylsilyloxy)but-2-en-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 2,2,6,6-四甲基哌啶氧化物 、 D-(-)-酒石酸二乙酯 、 碘苯二乙酸 作用下， 以 癸烷 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 (2S,3S)-3-((tert-butyldimethylsilyloxy)methyl)oxirane-2-carbaldehyde
  参考文献：
  名称：

  抗流感药（-）-oseltamivir游离碱和（-）-甲基3- epi- shikimate †的合成

  摘要：

  抗流感药物（-）-oseltamivir游离碱（7.1％的总产率; 98％ee）和3-- Epi- shikimate（-）-甲基-甲基（16％的总产率; 98％ee）的新对映体选择性合成从容易获得的原材料中进行描述。醛的无尖锐不对称环氧化和非对映选择性Barbier烯丙基化是手性结合过程中的关键反应，而环己烯羧酸酯核则是通过闭环易位反应构建的。

  DOI：

  10.1039/c2ob25635e

文献信息

• Taming the Friedel-Crafts Reaction: Organocatalytic Approach to Optically Active 2,3-Dihydrobenzofurans
  作者：Łukasz Albrecht、Lars Krogager Ransborg、Vibeke Lauridsen、Mette Overgaard、Theo Zweifel、Karl Anker Jørgensen

  DOI：10.1002/anie.201105819

  日期：2011.12.23

  Fine‐tuning: Three types of optically active trans‐2,3‐disubstituted‐2,3‐dihydrobenzofurans having three contiguous stereogenic centers can be efficiently accessed by one‐pot reaction cascades (see scheme; TMS=trimethylsilyl). High substitution diversity of the final products can be achieved from the same common precursors by fine‐tuning of their reactivity through simple structural modifications.

  微调：一锅反应级联可以有效地获得具有三个连续立体中心的三种类型的旋光反式2,3,3-二取代-2,3-二氢苯并呋喃（参见方案; TMS =三甲基甲硅烷基）。可以通过相同的常见前体通过简单的结构修饰来微调其反应性，从而实现最终产物的高取代多样性。
• Friedel-Crafts Reactions of Vinylaziridine Linked to an Ester Group
  作者：Shinji Nagumo、Hisashi Takada、Eiko Yasui、Yui Sahara、Yūki Chinen、Hirotoshi Tanaka、Yusuke Morita、Chihiro Kobiki、Daiki Narisawa、Megumi Mizukami、Masaaki Miyashita

  DOI：10.3987/com-10-12115

  日期：——

  Intermolecular Friedel-Crafts reactions of vinylaziridines 11, 12, 15, 16 and 20 linked. to an ester with various benzene 'derivatives occurred at the C4 position selectively to afford 5-amino-4-aryl-2-hexenoate derivatives in good yields.
• A study on the chelation control in the regioselective opening of 2,3-bifunctionalized epoxides
  作者：Giuliana Righi、Giovanna Pescatore、Francesco Bonadies、Carlo Bonini

  DOI：10.1016/s0040-4020(01)00492-6

  日期：2001.6

  The results obtained in the MgBr2-mediated opening of 2,3-bifunctionalized epoxides are reported. The studies showed that the chelation control of MgBr2 between different functionalities can in some cases be selective. (C) 2001 Elsevier Science Ltd. All rights reserved.
• 13-Demethyl-13-substituted-13,14-dihydroretinols as potential affinity labels of retinol-binding proteins: syntheses and stability studies
  作者：Revital Yefidoff、Limor Weiss、David Avisar、Amnon Albeck

  DOI：10.1016/j.bioorg.2003.09.002

  日期：2004.2

  13-Demethyl-13-substituted-13,14-dihydroretinois were synthesized and their stability under various conditions was measured in order to evaluate whether they would be useful as affinity labels of retinol binding proteins and retinol metabolizing enzymes. The 13-chloro analog could not be isolated because it eliminated HCl under the Wittig reaction conditions of its preparation. The trans- and cis-13,14-epoxy analogs are stable in non-protic organic solvents, but undergo an elimination reaction under various chromatographic conditions and in mixtures of organic solvents with water or alcohol. The 13-hydroxy and 13-methoxy analogs are stable in aqueous solutions and are therefore suitable for biological studies. (C) 2003 Elsevier Inc. All rights reserved.
• Influence of ester chain length, enzyme, and physical parameters on lipase-catalysed hydrolyses of meso-oxiranedimethanol esters. Part 2
  作者：Jonathan D Moseley、James Staunton

  DOI：10.1016/s0957-4166(00)00276-7

  日期：2000.8

  A range of meso-oxiranedimethanol diesters were prepared and subjected to hydrolysis by a selection of microbial and porcine-derived lipases. The best chain length was then subjected to a wider range of lipases. The physical reaction parameters were further investigated for the best enzyme/substrate combination. The results revealed the effects of ester chain length, choice of enzyme, and physical reaction parameters on the enzymic hydrolysis. Using a combination of the these three variables, it is demonstrated that this is a versatile approach for the optimisation of an enzymic hydrolysis for a given substrate. Additionally, we also report on an efficient, multigram synthesis of oxiranedimethanol diesters from cheap achiral precursors, their successful enzymic hydrolyses to alcohols in good chemical yield and e.e., and their conversion to synthetically useful aldehydes in high yield. Both enantiomeric series can readily be accessed from a single enzymic hydrolysis result. (C) 2000 Elsevier Science Ltd. All rights reserved.