benzyl 2-trimethylsilyl-2-oxoacetate | 443988-53-2

• 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-trimethylsilyl-2-oxoacetate
• 英文别名: Benzyl 2-oxo-2-trimethylsilylacetate
• CAS: 443988-53-2
• 化学式: C₁₂H₁₆O₃Si
• 分子量: 236.343
• InChiKey: UCIXSRKTCXULNS-UHFFFAOYSA-N

物化性质

• 沸点：
  298.2±33.0 °C(Predicted)
• 密度：
  1.052±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.18
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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-trimethylsilyl-2-oxoacetate 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 以78%的产率得到(+)-2-trimethylsilyl-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 diazoacetate 在 dirhodium tetraacetate 、 N,N-二异丙基乙胺 、 methyloxirane 作用下， 以 乙醚 、 甲苯 为溶剂， 生成 benzyl 2-trimethylsilyl-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。
• 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。
• Catalyst-free nucleophilic addition reactions of silyl glyoxylates in water
  作者：Man-Yi Han、Jing Lin、Wei Li、Wen-Yu Luan、Pei-Lin Mai、Yong Zhang

  DOI：10.1039/c7gc03775a

  日期：——

  of thiols to silyl glyoxylates was developed in water, providing an efficient route for the synthesis of α-hydroxysilanes. In the activation of silyl glyoxylates, hydrogen bonding is critical to the reaction, and rate acceleration was observed in water. Moreover, the competing Brook rearrangement was significantly suppressed with the assistance of water.

  在水中开发了一种新的无催化剂的巯基向乙醛酸甲硅烷基酯的加成反应，为合成α-羟基硅烷提供了一种有效的途径。在甲硅烷基乙醛酸酯的活化中，氢键对反应至关重要，并且在水中观察到速率加速。此外，在水的帮助下，竞争性布鲁克重排被显着抑制。
• Organocatalytic Asymmetric Vinylogous Aldol Reaction of Allyl Aryl Ketones to Silyl Glyoxylates
  作者：Man-Yi Han、Wen-Yu Luan、Pei-Lin Mai、Pinhua Li、Lei Wang

  DOI：10.1021/acs.joc.7b02546

  日期：2018.2.2

  A direct organocatalytic asymmetric vinylogous aldol reaction of allyl aryl ketones to silyl glyoxylates has been developed through the bifunctional catalyst, giving the α-hydroxysilanes with excellent enantioselectivity (up to 95% ee) and in high yields (up to 96%). The success of this catalytic methodology offers an opportunity to tackle the problems in the nucleophilic addition to acylsilanes. To

  通过双功能催化剂开发了烯丙基芳基酮与乙醛酸甲硅烷基酯的直接有机催化不对称乙烯基醇醛缩醛反应，使α-羟基硅烷具有出色的对映选择性（高达95％ee）和高产率（高达96％）。这种催化方法的成功提供了解决酰基硅烷亲核加成中的问题的机会。为了活化烯丙基芳基酮和酰基硅烷，在这种空前的转化中，所用的双官能催化剂是理想的有机催化剂。