benzyl 2-triethylsilyl-2-oxoacetate | 443988-54-3

• 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-oxoacetate
• 英文别名: Acetic acid, oxo(triethylsilyl)-, phenylmethyl ester；benzyl 2-oxo-2-triethylsilylacetate
• CAS: 443988-54-3
• 化学式: C₁₅H₂₂O₃Si
• 分子量: 278.423
• InChiKey: SVFKROHERZSFAP-UHFFFAOYSA-N

物化性质

• 沸点：
  347.2±35.0 °C(Predicted)
• 密度：
  1.015±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  19
• 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：
  43.4
• 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-oxoacetate 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 以85%的产率得到2-triethylsilyl-2-hydroxyacetic acid
  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：

  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

文献信息

• “On Water” Direct Catalytic Vinylogous Aldol Reaction of Silyl Glyoxylates
  作者：Hong Pan、Man-Yi Han、Pinhua Li、Lei Wang

  DOI：10.1021/acs.joc.9b01945

  日期：2019.11.1

  The unique reactivity of water in the direct catalytic vinylogous aldol reaction of silyl glyoxylates is reported. With the hydrogen-bonding networks from water, the unfavorable homogeneous reactions in organic solvents were severely suppressed, and the "on water" relay chemistry for the vinylogous aldol reaction was realized in heterogeneous conditions (water as solvent), providing the desired α-hydroxysilanes

  据报道，在乙醛酸甲硅烷基酯的直接催化乙烯基醇醛醇醛反应中，水具有独特的反应性。通过水与氢的键合网络，可以严重抑制有机溶剂中不利的均相反应，并且在非均相条件下（水为溶剂）实现了乙烯基醇醛醇缩醛反应的“水上”中继化学反应，从而提供了所需的α-羟基硅烷具有高产的季碳中心。此外，还展示了对水在生物系统中作用的新见解。
• Remote Stereoinduction in the Acylation of Fully Substituted Enolates: Tandem Reformatsky/Quaternary Claisen Condensations of Silyl Glyoxylates and β-Lactones
  作者：Stephen N. Greszler、Justin T. Malinowski、Jeffrey S. Johnson

  DOI：10.1021/ja108848d

  日期：2010.12.15

  glyoxylates and β-lactones to give highly functionalized Claisen condensation products. A heretofore undocumented instance of stereochemical 1,4-induction results in efficient transmission of β-lactone stereochemistry to the emerging fully substituted stereocenter. Second-stage transformations reveal that the five heteroatom-containing functionalities embedded within the products are entirely chemo-differentiated

  Reformatsky 试剂依次与乙醛酸甲硅烷基酯和 β-内酯反应，得到高度官能化的克莱森缩合产物。迄今为止未记录的立体化学 1,4-诱导实例导致 β-内酯立体化学有效传输到新兴的完全取代的立体中心。第二阶段的转化表明，嵌入产品中的五个含杂原子的功能是完全化学分化的，这种情况允许快速组装 leustroducsin B 核心亚结构。
• Highly Efficient Access to Both Geometric Isomers of Silyl Enol Ethers: Sequential 1,2-Brook/Wittig Reactions
  作者：Yuji Matsuya、Kentaro Wada、Daishiro Minato、Kenji Sugimoto

  DOI：10.1002/anie.201604945

  日期：2016.8.16

  2‐Brook/Wittig reactions were developed for the preparation of silyl enol ethers. This method enables highly selective preparation of both geometric isomers of glyoxylate silyl enol ethers, using aldehydes (E‐selective) and tosylimines (Z‐selective) as a Wittig electrophile. The salt‐free conditions of this reaction system are likely to be advantageous for switching the selectivity. The optimal reaction conditions

  开发了新的顺序1,2-Brook / Wittig反应，用于制备甲硅烷基烯醇醚。通过使用醛（E选择性）和甲苯磺胺（Z选择性）作为维蒂希亲电子试剂，该方法能够高度选择性地制备乙醛酸甲硅烷基烯醇醚的两种几何异构体。该反应系统的无盐条件可能对切换选择性有利。研究了最佳反应条件和反应的一般性，并讨论了观察到的选择性的合理解释。
• Organocatalyzed Direct Aldol Reaction of Silyl Glyoxylates for the Synthesis of α-Hydroxysilanes
  作者：Man-Yi Han、Xiaoyu Xie、Di Zhou、Pinhua Li、Lei Wang

  DOI：10.1021/acs.orglett.7b00811

  日期：2017.5.5

  A novel organocatalyzed direct aldol reaction of aldehydes to silyl glyoxylates is disclosed. This method provides an efficient route to α-hydroxysilanes with excellent enantioselectivities (up to 99% ee) and high diastereoselectivities (up to >20:1 dr). In the new activation model of silyl glyoxylates, the hydrogen bond is critical to the reaction. A carbonyl group directly attached to silicon in

  公开了醛到乙醛酸甲硅烷基酯的新颖的有机催化的直接醛醇缩合反应。该方法提供了一种具有优异对映选择性（高达99％ee）和高非对映选择性（高达> 20：1 dr）的高效生产α-羟基硅烷的途径。在新的甲硅烷基乙醛酸酯活化模型中，氢键对反应至关重要。可以通过氢键与羟基和羧酸的质子配位，活化直接连接到酰基硅烷中硅上的羰基。另外，可商购的顺式-升-4-羟脯氨酸是用于激活两个醛和acylsilanes理想的有机催化剂。
• Aqueous ZnCl₂ Complex Catalyzed Prins Reaction of Silyl Glyoxylates: Access to Functionalized Tertiary α-Silyl Alcohols
  作者：Man-Yi Han、Hong Pan、Pinhua Li、Lei Wang

  DOI：10.1021/acs.joc.9b03501

  日期：2020.5.1

  An efficient Prins reaction of silyl glyoxylates in the presence of an aqueous ZnCl2 complex as a catalyst was developed, providing functionalized tertiary α-silyl alcohols in high yields under mild conditions. A preliminary investigation indicated that the aqueous ZnCl2 complex acted as a dual functional catalyst of Brønsted and Lewis acid to activate the carbonyl groups of silyl glyoxylates via a

  开发了在水性ZnCl2络合物作为催化剂存在下，乙醛酸甲硅烷基酯的有效Prins反应，可在温和条件下以高收率提供官能化的叔α-甲硅烷基醇。初步研究表明，ZnCl2水溶液是布朗斯台德和路易斯酸的双重功能催化剂，可通过双重活化模型活化乙二醛基甲硅烷基化物的羰基。