(+/-)-N-[1-(methyldiphenylsilyl)-2-phenylethyl]acetamide

• 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: (+/-)-N-[1-(methyldiphenylsilyl)-2-phenylethyl]acetamide
• 英文别名: N-[1-[methyl(diphenyl)silyl]-2-phenylethyl]acetamide
• 化学式: C₂₃H₂₅NOSi
• 分子量: 359.543
• InChiKey: JXHBDUFRRGCXQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-N-[1-(methyldiphenylsilyl)-2-phenylethyl]acetamide 在 三氟甲磺酸 、 ammonium hydroxide 作用下， 以 二氯甲烷 为溶剂， 反应 5.33h， 生成 (+/-)-N-{1-[dihydroxy(methyl)silyl]-2-phenylethyl}acetamide
  参考文献：
  名称：

  Stereocontrolled Synthesis of Methyl Silanediol Peptide Mimics

  摘要：

  The treatment of chiral sulfinimines with (methyldiphenylsilyl)lithium gives alpha-(methyldiphenylsilyl)sulfinamides with excellent diastereoselectivity, and in good yield. The presence of alpha-protons on the imines is also well tolerated. The sulfinamide auxiliary is easily removed via treatment with methanolic HCl and the resulting amine extended into peptide chains accordingly. The diphenylsilyl moiety is a resilient protecting group for the corresponding silanediol, which can be unmasked via treatment with TfOH, followed by aqueous hydrolysis. The crude silanediol may be isolated and purified as its corresponding bis-TMS siloxane via protection with TMSCI, and converted back to the desired silanediol via hydrolysis with aqueous KOH. Efforts to apply this approach to biologically relevant silanediol peptide mimics, with a view to protease inhibition, are described.

  DOI：

  10.1021/jo701907d
• 作为产物：
  描述：

  (Z)-β-bromostyrene 在 copper(l) iodide 、 rhodium(II) acetate dimer 、 potassium carbonate 、 N,N-二甲基乙二胺 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 42.0h， 生成 (+/-)-N-[1-(methyldiphenylsilyl)-2-phenylethyl]acetamide
  参考文献：
  名称：

  Regioselective Rh(I)-Catalyzed Sequential Hydrosilylation toward the Assembly of Silicon-Based Peptidomimetic Analogues

  摘要：

  A highly regioselective Rh(I)-catalyzed hydrosilylation of enamides is presented. This mild protocol allows access to a wide variety of different arylsilanes with substitution at the beta-position of the enamide and functionalization on the alkyl chain tethered to the silane. This protocol is extended to include a sequential one-pot hydrosilylation. Using diphenylsilane as the appendage point, hydrosilylation of a protected allyl alcohol followed by hydrosilylation of an enamide generates a complex organosilane in one step. This highly convergent strategy to synthesize these functionalized systems now provides a way for the rapid assembly of a diverse collection of silane-based peptidomimetic analogues.

  DOI：

  10.1021/jo300904z

文献信息

• Stereocontrolled Synthesis of Methyl Silanediol Peptide Mimics
  作者：Lone Nielsen、Karl B. Lindsay、Jesper Faber、Niels Christian Nielsen、Troels Skrydstrup

  DOI：10.1021/jo701907d

  日期：2007.12.1

  The treatment of chiral sulfinimines with (methyldiphenylsilyl)lithium gives alpha-(methyldiphenylsilyl)sulfinamides with excellent diastereoselectivity, and in good yield. The presence of alpha-protons on the imines is also well tolerated. The sulfinamide auxiliary is easily removed via treatment with methanolic HCl and the resulting amine extended into peptide chains accordingly. The diphenylsilyl moiety is a resilient protecting group for the corresponding silanediol, which can be unmasked via treatment with TfOH, followed by aqueous hydrolysis. The crude silanediol may be isolated and purified as its corresponding bis-TMS siloxane via protection with TMSCI, and converted back to the desired silanediol via hydrolysis with aqueous KOH. Efforts to apply this approach to biologically relevant silanediol peptide mimics, with a view to protease inhibition, are described.
• Regioselective Rh(I)-Catalyzed Sequential Hydrosilylation toward the Assembly of Silicon-Based Peptidomimetic Analogues
  作者：Geanna K. Min、Troels Skrydstrup

  DOI：10.1021/jo300904z

  日期：2012.7.20

  A highly regioselective Rh(I)-catalyzed hydrosilylation of enamides is presented. This mild protocol allows access to a wide variety of different arylsilanes with substitution at the beta-position of the enamide and functionalization on the alkyl chain tethered to the silane. This protocol is extended to include a sequential one-pot hydrosilylation. Using diphenylsilane as the appendage point, hydrosilylation of a protected allyl alcohol followed by hydrosilylation of an enamide generates a complex organosilane in one step. This highly convergent strategy to synthesize these functionalized systems now provides a way for the rapid assembly of a diverse collection of silane-based peptidomimetic analogues.