Bis-((Z)-but-2-enyl)-(1,1-dimethyl-but-3-enyloxy)-silane | 445307-01-7

• 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: Bis-((Z)-but-2-enyl)-(1,1-dimethyl-but-3-enyloxy)-silane
• 英文别名: bis[(Z)-but-2-enyl]-(2-methylpent-4-en-2-yloxy)silane
• CAS: 445307-01-7
• 化学式: C₁₄H₂₆OSi
• 分子量: 238.445
• InChiKey: VBSMBAUKVLVTBM-LFPVQMOXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  一氧化碳 、 Bis-((Z)-but-2-enyl)-(1,1-dimethyl-but-3-enyloxy)-silane 在 acetylacetonatodicarbonylrhodium(l) 双氧水 、 碳酸氢钠 作用下， 以 苯 、 四氢呋喃 、 甲醇 为溶剂， 60.0 ℃ 、6.21 MPa 条件下， 反应 24.0h， 以65%的产率得到(4R,6S,7R)-2,7-Dimethyl-non-8-ene-2,4,6-triol
  参考文献：
  名称：

  Tandem silylformylation–allyl(crotyl)silylation: a new approach to polyketide synthesis

  摘要：

  Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford beta-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the similar to95degrees O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.04.004
• 作为产物：
  描述：

  dichloro-di-cis-crotylsilane 在 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 22.0h， 生成 Bis-((Z)-but-2-enyl)-(1,1-dimethyl-but-3-enyloxy)-silane
  参考文献：
  名称：

  Tandem silylformylation–allyl(crotyl)silylation: a new approach to polyketide synthesis

  摘要：

  Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford beta-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the similar to95degrees O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.04.004

文献信息

• Tandem Intramolecular Silylformylation−Crotylsilylation:  Highly Efficient Synthesis of Polyketide Fragments
  作者：Michael J. Zacuto、Steven J. O'Malle、James L. Leighton

  DOI：10.1021/ja026511y

  日期：2002.7.1

  Polyketide fragments may be rapidly and efficiently assembled in the tandem intramolecular silylformylation-crotylsilylation of alkenes and alkynes. The reactions establish up to three new stereocenters with good-to-excellent diastereoselectivity, and the use of the reaction in an iterative sense is demonstrated. In addition, a new dihydrosilane alcoholysis reaction has been developed, leading to a highly efficient sequence.
• Tandem silylformylation–allyl(crotyl)silylation: a new approach to polyketide synthesis
  作者：Michael J. Zacuto、Steven J. O'Malley、James L. Leighton

  DOI：10.1016/j.tet.2003.04.004

  日期：2003.11

  Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford beta-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the similar to95degrees O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. (C) 2003 Elsevier Ltd. All rights reserved.