(Z)-4-(Triisopropylsilyl)-4-(trimethylsilyl)-3-buten-2-ol | 141412-24-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-4-(Triisopropylsilyl)-4-(trimethylsilyl)-3-buten-2-ol
• 英文别名: (Z)-4-trimethylsilyl-4-tri(propan-2-yl)silylbut-3-en-2-ol
• CAS: 141412-24-0
• 化学式: C₁₆H₃₆OSi₂
• 分子量: 300.632
• InChiKey: PCLFDAUAMIIBHF-WJDWOHSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-4-(Triisopropylsilyl)-4-(trimethylsilyl)-3-buten-2-ol 在 Rh(norbornadiene)(bis(diphenylphosphino)butane)(+)BF4(-) 氢气 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以100%的产率得到(2R*,4S*)-4-(Triisopropylsilyl)-4-(trimethylsilyl)butan-2-ol
  参考文献：
  名称：

  Exploring the reactivity of alkenes bearing silicon and/or tin in the hydroxyl-directed hydrogenation. A diastereoselective synthesis of heterobimetallic compounds

  摘要：

  The hydroxyl-directed hydrogenation of (E)- and (Z)-gamma-hydroxy vinylstannanes and silanes has been studied in the presence of (dppb)Rh(NBD)BF4 (1). Efficient routes to gamma-hydroxy stannanes and silanes have been developed. Diastereoselectivities from 60 to >500:1 were observed. A significant difference in reaction rate and pathway was observed between the (E)- and (Z)-vinylstannanes. We observed a reductive destannation process for the (Z)-stannanes which was influenced by the size of the R group. Competition studies were carried out to determine if steric or electronic effects were responsible for the reactivity patterns observed.

  DOI：

  10.1021/jo00100a023
• 作为产物：
  描述：

  (Z)-4-(Tributylstannyl)-4-(trimethylsilyl)-3-buten-2-yl triisopropylsilyl ether 在 水 、 甲基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以97%的产率得到(Z)-4-(Triisopropylsilyl)-4-(trimethylsilyl)-3-buten-2-ol
  参考文献：
  名称：

  Studies in the Transmetalation of Cyclopropyl, Vinyl, and Epoxy Stannanes

  摘要：

  Diastereomerically pure cyclopropyl, vinyl, and epoxy stannanes have been converted to the corresponding organolithium species and trapped with a variety of electrophiles. The stereochemistry of the products was retained throughout the transmetalation-trapping sequence. The stereochemistry of the tributyltin moiety and the carbinol side chain was shown to have a dramatic influence on the rate of transmetalation. 1,4-Silyl migrations were observed for silicon groups of varying steric bulk, and crossover experiments showed the migration was an intramolecular process. Access to silanes which are difficult to prepare was achieved.

  DOI：

  10.1021/jo00118a043

文献信息

• Diastereoselectivity in the Cyclopropanation of 3,3-Bimetallic Allylic Alcohols. Preparation of Diastereomeric Cyclopropyl Carbinols via a Simple Oxidation-Reduction Sequence
  作者：Mark Lautens、Patrick H. M. Delanghe

  DOI：10.1021/jo00113a031

  日期：1995.4

  A highly diastereoselective cyclopropanation of allylic alcohols, containing a silyl and/or stannyl group using samarium/dihalomethane, provides a variety of bimetallic cyclopropane carbinols in good yield. A comparison with the more traditional Simmons-Smith conditions and its variants is made. The diastereoselectivity varies from 1:10 to >50:1 and depends on the substituents on the carbinol side chain (R-group) and on the substituents on the alkene portion of the allylic alcohol. Excellent diastereoselectivity (>50:1) was always obtained whenever a eis-substituent was present. Moreover, the minor diastereomer from the cyclopropanation can easily be obtained via a simple oxidation of the major cyclopropyl carbinol, followed by a selective reduction of the corresponding cyclopropyl ketone. Using LiAlH4 at 0 degrees C, facial selectivities of 15 to 20:1 are obtained for this reduction, while slightly higher selectivities up to (29:1) can be obtained using DIBAL-H. The combination of the cyclopropanation and oxidation/selective reduction sequence provides access to both diastereomeric bimetallic cyclopropanes.
• 1,4-Silyl migration reactions. Applicability to alkyl-, vinyl-, and cyclopropylsilanes
  作者：Mark Lautens、Patrick H. M. Delanghe、Jane Betty Goh、C. H. Zhang

  DOI：10.1021/jo00038a006

  日期：1992.6

  A series of silyl protected alcohols containing a tin substituent were found to undergo transmetalation followed by silyl migration from oxygen to carbon in the presence of methyllithium.
• Exploring the reactivity of alkenes bearing silicon and/or tin in the hydroxyl-directed hydrogenation. A diastereoselective synthesis of heterobimetallic compounds
  作者：Mark Lautens、C. H. Zhang、Betty Jane Goh、Cathleen M. Crudden、Marc J. A. Johnson

  DOI：10.1021/jo00100a023

  日期：1994.10

  The hydroxyl-directed hydrogenation of (E)- and (Z)-gamma-hydroxy vinylstannanes and silanes has been studied in the presence of (dppb)Rh(NBD)BF4 (1). Efficient routes to gamma-hydroxy stannanes and silanes have been developed. Diastereoselectivities from 60 to >500:1 were observed. A significant difference in reaction rate and pathway was observed between the (E)- and (Z)-vinylstannanes. We observed a reductive destannation process for the (Z)-stannanes which was influenced by the size of the R group. Competition studies were carried out to determine if steric or electronic effects were responsible for the reactivity patterns observed.
• Studies in the Transmetalation of Cyclopropyl, Vinyl, and Epoxy Stannanes
  作者：Mark Lautens、Patrick H. M. Delanghe、Jane B. Goh、C. H. Zhang

  DOI：10.1021/jo00118a043

  日期：1995.6

  Diastereomerically pure cyclopropyl, vinyl, and epoxy stannanes have been converted to the corresponding organolithium species and trapped with a variety of electrophiles. The stereochemistry of the products was retained throughout the transmetalation-trapping sequence. The stereochemistry of the tributyltin moiety and the carbinol side chain was shown to have a dramatic influence on the rate of transmetalation. 1,4-Silyl migrations were observed for silicon groups of varying steric bulk, and crossover experiments showed the migration was an intramolecular process. Access to silanes which are difficult to prepare was achieved.