(2R,3R)-3-((tert-butyldimethyisilyloxy)methyl)oxirane-2-carbaldehyde | 172586-64-0

• 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: (2R,3R)-3-((tert-butyldimethyisilyloxy)methyl)oxirane-2-carbaldehyde
• 英文别名: (2R,3R)-3-((tert-butyldimethylsilyloxy)methyl)oxirane-2-carbaldehyde；(2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]oxirane-2-carbaldehyde
• CAS: 172586-64-0
• 化学式: C₁₀H₂₀O₃Si
• 分子量: 216.352
• InChiKey: ZZEAXSVHLYHJBB-DTWKUNHWSA-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：

  (2R,3R)-3-((tert-butyldimethyisilyloxy)methyl)oxirane-2-carbaldehyde 在 氯化铵 、 N,N-二异丙基乙胺 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 ethyl (4R)-4-((2S,3R)-3-((tert-butyldimethylsilyloxy)methyl)oxiran-2-yl)-4-(methoxymethoxy)-2-methylenebutanoate
  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 、 L-(+)-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 (2R,3R)-3-((tert-butyldimethyisilyloxy)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

• [EN] PROCESS FOR THE PREPARATION OF OSELTAMIVIR AND METHYL 3-EPI-SHIKIMATE<br/>[FR] PROCÉDÉ POUR LA PRÉPARATION D'OSELTAMIVIR ET DE MÉTHYL 3-ÉPI-SHIKIMATE
  申请人：COUNCIL SCIENT IND RES

  公开号：WO2013061340A1

  公开（公告）日：2013-05-02

  The present invention discloses high yielding enantioselective process for synthesis of Oseltamivir from readily available starting material, cis-1,4-butene diol.The process features incorporation of chirality using sharpless asymmetric epoxidation(AE) and diastereoselective Barbier allylation and construction of cyclohexene carboxylic acid ester core through a ring closing metathesis (RCM) reaction. Further also disclosed herein is synthesis of (-)-methyl 3-epi-shikimate.

  本发明揭示了一种高产高对映选择性的奥司他韦合成工艺，从易得的起始物质顺式-1,4-丁二醇开始。该工艺采用Sharpless不对称环氧化（AE）和对映选择性Barbier烯丙基化，通过环闭合醚交换反应（RCM）构建环己烯羧酸酯核心来引入手性。此外，还披露了(-)-甲基3-epi-香槟酸的合成。
• PROCESS FOR THE PREPARATION OF OSELTAMIVIR AND METHYL 3-EPI-SHIKIMATE
  申请人：Council of Scientific & Industrial Research

  公开号：US20140243537A1

  公开（公告）日：2014-08-28

  The present invention discloses high yielding enantioselective process for synthesis of Oseltamivir from readily available starting material, cis-1,4-butene diol. The process features incorporation of chirality using sharpless asymmetric epoxidation (AE) and diastereoselective Barbier allylation and construction of cyclohexene carboxylic acid ester core through a ring closing metathesis (RCM) reaction. Further also disclosed herein is synthesis of (−)-methyl 3-epi-shikimate.

  本发明揭示了一种高产高对映选择性的奥司他韦合成工艺，从易得的起始物质顺式-1,4-丁二醇出发。该工艺采用Sharpless不对称环氧化（AE）和立体选择性的Barbier烯丙基化，通过环内酯交换反应（RCM）构建环己烯羧酸酯核心以引入手性。此外，还揭示了(−)-甲基3-epi-香椿糖酸的合成。
• Optically Active Thiophenes via an Organocatalytic One-Pot Methodology
  作者：Lars Krogager Ransborg、Łukasz Albrecht、Christian F. Weise、Jesper R. Bak、Karl Anker Jørgensen

  DOI：10.1021/ol203237r

  日期：2012.2.3

  A general methodology for the synthesis of trisubstituted, optically active thiophenes by an organocatalytic one-pot reaction cascade is presented. The target products are synthesized in good yields (up to 92%) and with excellent enantioselectivities (up to 98% ee). Importantly, based on practical and easily available starting materials, the presented methodology can be conducted under mild reaction conditions. To further elucidate the generality, the synthesis of optically active thienoindoles, as well as selenophenes, is also demonstrated.
• Chelation control associated with organometallic addition reactions in water. The high stereoselectivity offered by α- and β-hydroxyl substituents obviates the need for protecting groups
  作者：L Paquette

  DOI：10.1016/00404-0399(50)1439o-

  日期：1995.9.18

  High stereoselectivities have been observed for indium-promoted allylations of alpha- and beta-hydroxy aldehydes in aqueous media, with strong implication that chelate control can continue to operate in water.
• Tandem Enyne Metathesis−Metallotropic [1,3]-Shift for a Concise Total Syntheses of (+)-Asperpentyn, (−)-Harveynone, and (−)-Tricholomenyn A
  作者：Jingwei Li、Sangho Park、Reagan L. Miller、Daesung Lee

  DOI：10.1021/ol802675j

  日期：2009.2.5

  A tandem reaction sequence involving relay metathesis-induced enyne RCM and metallotropic [1,3]-shift is an effective tool to construct cyclic alkenes with embedded 1,5-dien-3-yne moieties from acyclic precursors containing a 1,3-diyne. Total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A have been accomplished by implementing this metathesis-based tandem reaction sequence as the key step.