(tert-butyl)dimethyl(phenylacetyl)silane | 132150-43-7

• 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: (tert-butyl)dimethyl(phenylacetyl)silane
• 英文别名: 1-[tert-Butyl(dimethyl)silyl]-2-phenylethan-1-one；1-[tert-butyl(dimethyl)silyl]-2-phenylethanone
• CAS: 132150-43-7
• 化学式: C₁₄H₂₂OSi
• 分子量: 234.414
• InChiKey: WRMUJIBIWHKJKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (tert-butyl)dimethyl(phenylacetyl)silane 在 六甲基磷酰三胺 、 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (Z)-methyl 3-(tert-butyldimethylsilyl)-2-methyl-4-phenyl-2-butenoate
  参考文献：
  名称：

  通过提供多取代烯烃的 Ynolate 阴离子对酰基硅烷进行 Z 选择性烯烃化的第一种通用方法

  摘要：

  我们开发了第一个通用方法，通过烯醇化物阴离子对酰基硅烷进行立体选择性烯化，以产生 (Z)-β-甲硅烷基-α，β-不饱和酯，从而产生三和四取代的烯烃。

  DOI：

  10.1021/ja026275r
• 作为产物：
  描述：

  2-benzyl-1,3-dithiane 在 正丁基锂 、 mercury dichloride 、 cadmium(II) chloride 作用下， 以 四氢呋喃 、 水 、 丙酮 、 甲苯 、 正戊烷 为溶剂， 反应 24.0h， 生成 (tert-butyl)dimethyl(phenylacetyl)silane
  参考文献：
  名称：

  A Novel Stereoselective Reaction Cascade Leading fromα-Silylated Allylic Alcohols to Aldol-Type Products

  摘要：

  The treatment of alpha-silylated allylic alcohols with epoxidizing reagents afforded in a highly stereocontrolled fashion a-silylated aldols. The transformation is proposed to proceed either by a reaction cascade involving stereospecific epoxidation of the allylic-alcohol moiety followed by an acid-supported pinacol-type rearrangement, or by a sequence consisting of a pi-face-selective electrophilic attack at the allylic silane moiety with hyperconjugative stabilization of the evolving carbocation, followed by rearrangement of the thus obtained pentacoordinated silanium ion (see Scheme 3). Depending on the reaction conditions, the pi-face selectivity of the oxidation step is controlled by the: stereogenic C-atom or the more remote Si-center of chirality.

  DOI：

  10.1002/(sici)1522-2675(19990407)82:4<561::aid-hlca561>3.0.co;2-u

文献信息

• Evaluation of C-trialkylsilyl enol and thioenol ethers as intermediates in the synthesis of acylsilanes
  作者：Catherine Hammaecher、Imad Ouzzane、Charles Portella、Jean-Philippe Bouillon

  DOI：10.1016/j.tet.2004.10.082

  日期：2005.1

  C-silyl enol ethers or thioenol ethers have been prepared by a Peterson reaction, as intermediates for acylsilane synthesis. Bis(trialkylsilyl)(methoxy)- or -(methylsulfanyl)methanes bearing identical or different trialkylsilyl groups were used as starting materials in order to assess the selectivity of the Peterson elimination step. A good selectivity was observed only with ethers bearing the TMS

  通过Peterson反应已经制备了C-甲硅烷基烯醇醚或硫烯醇醚，作为酰基硅烷合成的中间体。为了评估彼得森消除步骤的选择性，将带有相同或不同三烷基甲硅烷基的双（三烷基甲硅烷基）（甲氧基）-或-（甲基硫烷基）甲烷用作起始原料。仅用带有TMS和TBDMS基团的醚观察到良好的选择性。然而，由于难以以正确的产率获得这些试剂，因此没有实际的兴趣来使用这些试剂。事实证明，双（三甲基甲硅烷基）（甲基硫烷基）甲烷是制备C-甲硅烷基硫烯醇醚的良好试剂，C-甲硅烷基硫烯醇醚在传统的酸性条件下可以水解，从而以合理的总收率得到酰基硅烷。该方便的过程扩展到双（酰基硅烷）的合成。
• A Novel Stereoselective Reaction Cascade Leading fromα-Silylated Allylic Alcohols to Aldol-Type Products
  作者：Jürg Fässler、Valentin Enev、Stefan Bienz

  DOI：10.1002/(sici)1522-2675(19990407)82:4<561::aid-hlca561>3.0.co;2-u

  日期：1999.4.7

  The treatment of alpha-silylated allylic alcohols with epoxidizing reagents afforded in a highly stereocontrolled fashion a-silylated aldols. The transformation is proposed to proceed either by a reaction cascade involving stereospecific epoxidation of the allylic-alcohol moiety followed by an acid-supported pinacol-type rearrangement, or by a sequence consisting of a pi-face-selective electrophilic attack at the allylic silane moiety with hyperconjugative stabilization of the evolving carbocation, followed by rearrangement of the thus obtained pentacoordinated silanium ion (see Scheme 3). Depending on the reaction conditions, the pi-face selectivity of the oxidation step is controlled by the: stereogenic C-atom or the more remote Si-center of chirality.
• The First General Method for<i> Z</i>-Selective Olefination of Acylsilanes via Ynolate Anions Providing Multisubstituted Alkenes
  作者：Mitsuru Shindo、Kenji Matsumoto、Seiji Mori、Kozo Shishido

  DOI：10.1021/ja026275r

  日期：2002.6.1

  We have developed the first general method for a stereoselective olefination of acylsilanes via ynolate anions to produce (Z)-beta-silyl-alpha,beta-unsaturated ester, which leads to tri- and tetrasubstituted alkenes.

  我们开发了第一个通用方法，通过烯醇化物阴离子对酰基硅烷进行立体选择性烯化，以产生 (Z)-β-甲硅烷基-α，β-不饱和酯，从而产生三和四取代的烯烃。