2-methyl-4-<(trimethylsilyl)oxy>-2-pentene | 86370-82-3

• 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: 2-methyl-4-<(trimethylsilyl)oxy>-2-pentene
• 英文别名: Trimethyl[(4-methylpent-3-en-2-yl)oxy]silane；trimethyl(4-methylpent-3-en-2-yloxy)silane
• CAS: 86370-82-3
• 化学式: C₉H₂₀OSi
• 分子量: 172.343
• InChiKey: ITFNGWUBNSROKN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-4-<(trimethylsilyl)oxy>-2-pentene 在 二甲基二环氧乙烷 作用下， 以 丙酮 为溶剂， 生成 [(S)-1-((S)-3,3-Dimethyl-oxiranyl)-ethoxy]-trimethyl-silane 、 [(R)-1-((S)-3,3-Dimethyl-oxiranyl)-ethoxy]-trimethyl-silane
  参考文献：
  名称：

  Solvent Effects in the Regio- and Diastereoselective Epoxidations of Acyclic Allylic Alcohols by Dimethyldioxirane:  Hydrogen Bonding as Evidence for a Dipolar Transition State

  摘要：

  A mechanistically significant solvent effect is observed in the regioselectivity of the geraniol epoxidation by dimethyldioxirane. In hydrogen-bonding solvents (MeOH), the 6,7-epoxide is preferred over the 2,3-epoxide (74:26), which reveals that the more nucleophilic 6,7 double bond (the 2,3 double bond is inductively deactivated by the allylic hydroxy group) is preferentially attacked by the electrophilic dimethyldioxirane. In MeOH, both regioisomeric dipolar transition states are equally well stabilized by interaction through intermolecular hydrogen bonding with solvent molecules. In the nonpolar CCl4, intramolecular hydrogen bonding with the allylic hydroxy functionality favors attack at the 2,3 double bond and proportionally more 2,3-epoxide is formed. Similarly, also the pi-facial selectivity in the dimethyldioxirane epoxidation of methyl-substituted chiral acyclic allylic alcohols is controlled by intermolecular versus intramolecular hydrogen bonding. Thus, higher three selectivities are obtained in the nonpolar CCl4 by stabilization of the diastereomeric transition state with minimal allylic strain through intramolecular hydrogen bonding with the allylic hydroxy group. The geometry of the dipolar transition state for the dimethyldioxirane epoxidations is similar to that of m-CPBA, but with apparently a slightly larger (ca. 130 degrees) dihedral angle alpha to relieve 1,2-allylic strain.

  DOI：

  10.1021/jo951984r

文献信息

• Hydroxy-directed regio-diastereoselective ene reaction of singlet oxygen with chiral allylic alcohols
  作者：Waldemar Adam、Bernd Nestler

  DOI：10.1021/ja00065a013

  日期：1993.6

  The photooxygenation of chiral allylic alcohols 1a, (Z)-1f-k, ethers 1b-d, and acetate 1e gave the corresponding hydroperoxy homoallylic alcohols and derivatives 2 through the ene reaction with singlet oxygen. While the reaction of the acetate 1e proceeded erythro-diastereoselectively as a result of the classical cis effect, for the allylic alcohols 1a and (Z)-1f-k, in which an alkyl group is located

  手性烯丙醇 1a、(Z)-1f-k、醚 1b-d 和乙酸酯 1e 的光氧化反应通过与单线态氧的烯反应得到相应的氢过氧高烯丙醇和衍生物 2。由于经典的顺式效应，乙酸酯 1e 的反应以赤型非对映选择性进行，对于烯丙醇 1a 和 (Z)-1f-k，其中烷基位于带羟基的取代基的顺式，高观察到threo选择性。这一发现可以通过立体中心的亲核羟基官能团与进入的亲电子单线态氧亲烯体的配位来解释
• HIYAMA, TAMEJIRO;OBAYASHI, MICHIO, TETRAHEDRON LETT., 1983, 24, N 4, 395-398
  作者：HIYAMA, TAMEJIRO、OBAYASHI, MICHIO

  DOI：——

  日期：——
• Solvent Effects in the Regio- and Diastereoselective Epoxidations of Acyclic Allylic Alcohols by Dimethyldioxirane:  Hydrogen Bonding as Evidence for a Dipolar Transition State
  作者：Waldemar Adam、Alexander K. Smerz

  DOI：10.1021/jo951984r

  日期：1996.1.1

  A mechanistically significant solvent effect is observed in the regioselectivity of the geraniol epoxidation by dimethyldioxirane. In hydrogen-bonding solvents (MeOH), the 6,7-epoxide is preferred over the 2,3-epoxide (74:26), which reveals that the more nucleophilic 6,7 double bond (the 2,3 double bond is inductively deactivated by the allylic hydroxy group) is preferentially attacked by the electrophilic dimethyldioxirane. In MeOH, both regioisomeric dipolar transition states are equally well stabilized by interaction through intermolecular hydrogen bonding with solvent molecules. In the nonpolar CCl4, intramolecular hydrogen bonding with the allylic hydroxy functionality favors attack at the 2,3 double bond and proportionally more 2,3-epoxide is formed. Similarly, also the pi-facial selectivity in the dimethyldioxirane epoxidation of methyl-substituted chiral acyclic allylic alcohols is controlled by intermolecular versus intramolecular hydrogen bonding. Thus, higher three selectivities are obtained in the nonpolar CCl4 by stabilization of the diastereomeric transition state with minimal allylic strain through intramolecular hydrogen bonding with the allylic hydroxy group. The geometry of the dipolar transition state for the dimethyldioxirane epoxidations is similar to that of m-CPBA, but with apparently a slightly larger (ca. 130 degrees) dihedral angle alpha to relieve 1,2-allylic strain.