(methyldiphenylsilyl)acetic acid

• 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: (methyldiphenylsilyl)acetic acid
• 英文别名: diphenylmethylsilylacetic acid；2-(methyldiphenylsilyl)acetic acid；Ph2(Me)SiCH2CO2H；2-[methyl(diphenyl)silyl]acetic acid
• 化学式: C₁₅H₁₆O₂Si
• 分子量: 256.376
• InChiKey: NGMMHYJZLUDWJD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (methyldiphenylsilyl)acetic acid 在 potassium hydroxide 作用下， 以 甲醇 、 乙腈 为溶剂， 以71%的产率得到1,2-bis[diphenyl(methyl)silyl]ethane
  参考文献：
  名称：

  Electrochemical Synthesis of 1,2-Disilylethanes from α-Silylacetic Acids

  摘要：

  The synthesis of 1,2-disilylethanes [R1R2R3Si-(CH2)(2)SiR1R2R3] is usually conducted by using noble metal reagents or catalysts. This work describes a new electrochemical synthetic method for their preparation in good yields by oxidation of alpha-silylacetic acids at Pt anodes (Kolbe electrolysis). Most of the reported synthesized 1,2-disilylethanes in this work are unknown.

  DOI：

  10.1021/jo200254z
• 作为产物：
  描述：

  甲基二苯基氯硅烷 在 lithium diisopropyl amide 作用下， 反应 4.0h， 生成 (methyldiphenylsilyl)acetic acid
  参考文献：
  名称：

  Electrochemical Synthesis of 1,2-Disilylethanes from α-Silylacetic Acids

  摘要：

  The synthesis of 1,2-disilylethanes [R1R2R3Si-(CH2)(2)SiR1R2R3] is usually conducted by using noble metal reagents or catalysts. This work describes a new electrochemical synthetic method for their preparation in good yields by oxidation of alpha-silylacetic acids at Pt anodes (Kolbe electrolysis). Most of the reported synthesized 1,2-disilylethanes in this work are unknown.

  DOI：

  10.1021/jo200254z

文献信息

• A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions
  作者：Yihong Wang、Claire M. Young、Honglei Liu、Will C. Hartley、Max Wienhold、David. B. Cordes、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1002/anie.202208800

  日期：2022.9.19

  The catalytic generation of unsubstituted and alkyl substituted C(1)-ammonium enolates from α-silyl-α-alkyl substituted carboxylic acids using the isothiourea HyperBTM has been developed and applied in enantioselective [2+2]-cycloaddition reactions.

  使用异硫脲 HyperBTM 从 α-甲硅烷基-α-烷基取代的羧酸催化生成未取代和烷基取代的 C(1)-烯醇化铵已被开发并应用于对映选择性 [2+2]-环加成反应。
• Probing Regio- and Enantioselectivity in the Formal [2 + 2] Cycloaddition of C(1)-Alkyl Ammonium Enolates with β- and α,β-Substituted Trifluoromethylenones
  作者：Yihong Wang、Claire M. Young、David B. Cordes、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1021/acs.joc.2c02688

  日期：2023.6.16

  on both reaction components. Solely [2 + 2] cycloaddition products are observed when using α,β-substituted trifluoromethylenones or α-trialkylsilyl acetic acid derivatives; both [2 + 2] and [4 + 2] cycloaddition products are observed when using β-substituted trifluoromethylenones and α-alkyl-α-trialkylsilyl acetic acids as reactants, with the [2 + 2] cycloaddition as the major reaction product. The beneficial

  已开发出异硫脲催化的 C(1)-烷基和 C(1)-未取代的烯醇铵与 β- 和 α,β-取代的三氟亚甲基酮的区域和对映选择性形式 [2 + 2] 环加成反应。在所有情况下，观察到[2 + 2]-环加成优先于替代的[4 + 2]-环加成，使β-内酯具有优异的非对映选择性和对映选择性（34个例子，高达>95:5 dr，>99： 1 呃）。该过程的区域选择性取决于两种反应组分上取代基的性质。当使用α,β-取代的三氟亚甲基酮或α-三烷基甲硅烷基乙酸衍生物时，仅观察到[2+2]环加成产物；当使用β-取代的三氟亚甲基酮和α-烷基-α-三烷基甲硅烷基乙酸作为反应物时，观察到[2+2]和[4+2]环加成产物，以[2+2]环加成作为主要反应产物。该方案中酸组分内的 α-甲硅烷基取代基的有益作用已通过对照实验得到证明。
• A convenient method for the synthesis of α-silylacetic acids
  作者：Alex V. Shtelman、James Y. Becker

  DOI：10.1016/j.tetlet.2008.03.050

  日期：2008.5

  A method is described for the preparation of alpha-silylacetic acids of the type R(3)SiCH(2)CO(2)H by treating trimethylsilyl acetate with LDA followed by quenching with chlorosilanes. (C) 2008 Elsevier Ltd. All rights reserved.
• Synthesis of α-silylcarboxylic acids
  作者：Alex V. Shtelman、James Y. Becker

  DOI：10.1016/j.tet.2010.12.020

  日期：2011.2

  New alpha-silylacetic acids have been prepared following a general and convenient procedure of a one-pot reaction between trimethylsilylacetate and different chlorosilanes. New derivatives of diphenyl(methyl) silylacetic acid were prepared by a direct alkylation of its dianion with benzyl-, allyl-, and alkyl halides and trimethylchlorogermane to afford new alpha-silylcarboxylic acids. (C) 2010 Elsevier Ltd. All rights reserved.
• Synthesis of α-germyl and α-silylcarboxylic acids and selected electrochemical oxidations
  作者：Anna Rakovshik、Alex V. Shtelman、James Y. Becker

  DOI：10.1016/j.jorganchem.2011.12.025

  日期：2012.6

  New alpha-germylcarboxylic acids, alpha-silyl-alpha-halocarboxylic and alpha-silyl-alpha-alkylcarboxylic acids including some known alpha-silyl(cycloalkyl)carboxylic acids have been prepared by different synthetic methods. The anodic oxidation in basic methanol of selected examples of these acids has been investigated under various experimental conditions to afford mainly oxidative degermylation/desilylation and decarboxylation products. Based on the emerged products, various mechanisms are suggested and discussed. (C) 2011 Elsevier B. V. All rights reserved.