methyl 3E-2-(dimethyl(phenyl)silyl)pent-3-enoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3E-2-(dimethyl(phenyl)silyl)pent-3-enoate
• 英文别名: methyl (E)-2-[dimethyl(phenyl)silyl]pent-3-enoate
• 化学式: C₁₄H₂₀O₂Si
• 分子量: 248.397
• InChiKey: NPJWUVKRDHXVDR-WEVVVXLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 3E-2-(dimethyl(phenyl)silyl)pent-3-enoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (R)-2-(dimethyl(phenyl)silyl)pent-3-en-1-ol
  参考文献：
  名称：

  Vinylogous Aldol Products from Chiral Crotylsilanes Obtained by Enantioselective Rh(II) and Cu(I) Carbenoid Si−H Insertion

  摘要：

  Enantioenriched homoallylic ethers containing a alpha,beta-unsaturated ester (syn-vinylogous aldol products) were directly accessed by Lewis acid catalyzed crotylation utilizing chiral silane 2. The reagents were prepared by enantioselective Si-H Insertion to an alpha-diazovinylacetates using Davies' Rh-2(DOSP)(4) catalyst or chiral Cu(I) Schiff base complex.

  DOI：

  10.1021/ol100604m
• 作为产物：
  描述：

  3-戊烯酸 在 dirhodium tetraacetate 、 ABSA 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.83h， 生成 methyl 3E-2-(dimethyl(phenyl)silyl)pent-3-enoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j

文献信息

• UNO HIDEMITSU, BULL. CHEM. SOC. JAP., 59,(1986) N 8, 2471-2479
  作者：UNO HIDEMITSU

  DOI：——

  日期：——
• A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds
  作者：Priyadarshanie Bulugahapitiya、Yannick Landais、Liliana Parra-Rapado、Denis Planchenault、Valéry Weber

  DOI：10.1021/jo961952j

  日期：1997.3.1

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.
• Vinylogous Aldol Products from Chiral Crotylsilanes Obtained by Enantioselective Rh(II) and Cu(I) Carbenoid Si−H Insertion
  作者：Jie Wu、Yu Chen、James S. Panek

  DOI：10.1021/ol100604m

  日期：2010.5.7

  Enantioenriched homoallylic ethers containing a alpha,beta-unsaturated ester (syn-vinylogous aldol products) were directly accessed by Lewis acid catalyzed crotylation utilizing chiral silane 2. The reagents were prepared by enantioselective Si-H Insertion to an alpha-diazovinylacetates using Davies' Rh-2(DOSP)(4) catalyst or chiral Cu(I) Schiff base complex.