benzyl 2-triethylsilyl-2-diazoacetate | 443988-47-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl 2-triethylsilyl-2-diazoacetate
• 英文别名: benzyl 2-triethyl-2-diazoacetate；Benzyl 2-diazo-2-triethylsilylacetate
• CAS: 443988-47-4
• 化学式: C₁₅H₂₂N₂O₂Si
• 分子量: 290.437
• InChiKey: XYFMLUWBIJTIPW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl 2-triethylsilyl-2-diazoacetate 在 dirhodium tetraacetate 、 methyloxirane 作用下， 以 甲苯 为溶剂， 以89%的产率得到benzyl 2-triethylsilyl-2-oxoacetate
  参考文献：
  名称：

  Synthesis and Use of α-Silyl-Substituted α-Hydroxyacetic Acids

  摘要：

  Rhodium-catalyzed oxygen transfer was used to generate benzyl 2-sifyi-2-oxoacetates in good yields. The hydrogenation of these compounds led to chiral alpha-silyl-substituted a-hydroxyacetic acids. Resolution by means of HPLC using a chiral stationary phase afforded an enantiomerically pure representative of this class of compounds, which was successfully applied as a chiral ligand in an asymmetric aldol-type reaction.

  DOI：

  10.1021/ol025911n
• 作为产物：
  描述：

  三乙基硅基三氟甲磺酸酯 、 benzyl diazoacetate 在 N,N-二异丙基乙胺 作用下， 以 乙醚 为溶剂， 以92%的产率得到benzyl 2-triethylsilyl-2-diazoacetate
  参考文献：
  名称：

  Synthesis and Use of α-Silyl-Substituted α-Hydroxyacetic Acids

  摘要：

  Rhodium-catalyzed oxygen transfer was used to generate benzyl 2-sifyi-2-oxoacetates in good yields. The hydrogenation of these compounds led to chiral alpha-silyl-substituted a-hydroxyacetic acids. Resolution by means of HPLC using a chiral stationary phase afforded an enantiomerically pure representative of this class of compounds, which was successfully applied as a chiral ligand in an asymmetric aldol-type reaction.

  DOI：

  10.1021/ol025911n

文献信息

• Intermolecular Rhodium(II)-Catalyzed Reactions with Silicon-Substituted Carbonyl Ylides
  作者：Carsten Bolm、Sandra Saladin、Andrey Kasyan

  DOI：10.1021/ol026987m

  日期：2002.12.1

  [reaction: see text] The Rh(II)-catalyzed reaction of benzyl 2-trialkylsilyl-2-diazoacetates with various acyclic and cyclic ketones affords novel dioxolanones via silicon-substituted carbonyl ylides in up to 98% yield.

  [反应：见正文] 2-甲基三烷基甲硅烷基-2-重氮乙酸苄酯与各种无环和环状酮的Rh（II）催化反应可通过硅取代的羰基化物以高达98％的产率提供新型的二氧戊环酮。
• The rhodium-catalysed synthesis of pyrrolidinone-substituted (trialkylsilyloxy)acrylic esters
  作者：Daniel L. Priebbenow、Carsten Bolm

  DOI：10.1039/c3ra41527a

  日期：——

  A method for the preparation of novel pyrrolidine substituted (trialkylsilyloxy)acrylic esters has been developed. The protocol involves a rhodium-catalysed O-insertion/rearrangement reaction between N-functionalised 2-pyrrolidinones and α-silyl α-diazoacetates to form the corresponding acrylic esters in moderate to high yields.

  已经开发了一种制备新型吡咯烷取代的（三烷基甲硅烷基氧基）丙烯酸酯的方法。该方案涉及在N-官能化的2-吡咯烷酮和α-甲硅烷基α-二重氮乙酸酯之间的铑催化的O-插入/重排反应，以中等至高产率形成相应的丙烯酸酯。
• Enantiopure α-Silyl-Substituted α-Hydroxyacetic Acids Using O-H Insertion Methodology and Boron-Based Asymmetric Reductions
  作者：Carsten Bolm、Sandra Saladin、Arno Claßen、Andrey Kasyan、Elisabetta Veri、Gerhard Raabe

  DOI：10.1055/s-2005-862369

  日期：——

  Two routes to optically active α-silyl-substituted α-hydroxyacetic acids are described. As a key step, the first utilizes O-H insertion reactions of (R)-and (S)-phenylethanol into benzyl 2-silyl-2-diazoacetates in the presence of [Rh2(OAc)4]. Alternatively, asymmetric reductions of benzyl 2-silyl-2-oxoacetates using (R)-Alpine-Borane® afford the corresponding α-hydroxy esters with up to 91% ee.

  描述了两种合成光学活性α-硅基取代的α-羟基乙酸的方法。作为关键步骤，第一种方法利用(R)-和(S)-苯乙醇在[Rh2(OAc)4]的存在下与苄基2-硅基-2-叠氮乙酸酯的O-H插入反应。另一种方法则是使用(R)-阿尔卑斯硼烷®对苄基2-硅基-2-氧乙酸酯进行不对称还原，从而获得对应的α-羟基酯，的光学纯度可达到91% ee。