di-(Z)-but-2-enylsilane | 445306-99-0

• 分子结构分类: 有机化合物
• 英文名称: di-(Z)-but-2-enylsilane
• 英文别名: di(cis-crotyl)silane；di-cis-crotylsilane
• CAS: 445306-99-0
• 化学式: C₈H₁₆Si
• 分子量: 140.301
• InChiKey: NGCZMJRWYQUCLB-GLIMQPGKSA-N

物化性质

• 沸点：
  55 °C(Press: 15 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  9.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-methyl-5-hexyn-3-ol 、 di-(Z)-but-2-enylsilane 在 sodium hydride 作用下， 以 正己烷 为溶剂， 生成 Bis-((Z)-but-2-enyl)-(1-isopropyl-but-3-ynyloxy)-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
• 作为产物：
  描述：

  dichloro-di-cis-crotylsilane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 以5.5 g的产率得到di-(Z)-but-2-enylsilane
  参考文献：
  名称：

  Tandem Intramolecular Silylformylation−Crotylsilylation:  Highly Efficient Synthesis of Polyketide Fragments

  摘要：

  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.

  DOI：

  10.1021/ja026511y

文献信息

• An “Aprotic” Tamao Oxidation/<i>Syn</i>-Selective Tautomerization Reaction for the Efficient Synthesis of the C(1)–C(9) Fragment of Fludelone
  作者：Tyler J. Harrison、Philippe M. A. Rabbat、James L. Leighton

  DOI：10.1021/ol302221s

  日期：2012.9.21

  An efficient synthesis of the C(1)–C(9) fragment of fludelone has been developed. The key step is a tandem silylformylation–crotylsilylation/Tamao oxidation sequence that establishes the C(5) ketone, the C(6), C(7), and C(8) stereocenters, and the C(9) alkene in a single operation from a readily accessed starting material. The stereochemical outcome at C(6) depends critically on the development of

  已开发出氟地酮 C(1)–C(9) 片段的有效合成。关键步骤是串联甲硅烷基化-巴豆基甲硅烷基化/Tamao 氧化序列，该序列在单个化合物中建立 C(5) 酮、C(6)、C(7) 和 C(8) 立体中心以及 C(9) 烯烃从易于获取的起始材料操作。C(6) 的立体化学结果关键取决于“非质子”Tamao 氧化的发展，这会导致使用“标准”Tamao 氧化条件观察到的内在非对映选择性发生逆转。
• Synthesis and Evaluation of a Linkable Functional Group-Equipped Analogue of the Epothilones
  作者：Corinne N. Foley、Liang-An Chen、Dan L. Sackett、James L. Leighton

  DOI：10.1021/acsmedchemlett.7b00131

  日期：2017.7.13

  family of microtubule-stabilizing agents is reported. An analogue of epothilone B in which the C(6) methyl group has been replaced with a 4-azidobutyl group has been prepared by total chemical synthesis, and amides derived from the azido group have been shown to retain the activity of the parent compound. These results set the stage for an evaluation of the potential of the epothilones to serve as the drug

  报道了一种用于埃博霉素微管稳定剂家族的接头策略的验证方法。通过全化学合成制备了埃坡霉素B的类似物，其中的C（6）甲基已被4-叠氮基丁基取代，并且已证明衍生自叠氮基的酰胺保留了母体化合物的活性。这些结果为评价埃博霉素作为抗体-药物结合物和其他选择性靶向肿瘤细胞的结合物的药物成分的潜力奠定了基础。
• Toward More “Ideal” Polyketide Natural Product Synthesis: A Step-Economical Synthesis of Zincophorin Methyl Ester
  作者：Tyler J. Harrison、Stephen Ho、James L. Leighton

  DOI：10.1021/ja201467z

  日期：2011.5.18

  A highly efficient and step-economical synthesis of zincophorin methyl ester has been achieved. The unprecedented step economy of this zincophorin synthesis is principally due to an application of the tandem silylformylation-crotylsilylation/Tamao oxidation-diastereoselective tautomerization reaction, which achieves in a single step what would typically require a significant multistep sequence.

  实现了锌基蛋白甲酯的高效、一步经济合成。这种锌蛋白合成的前所未有的步骤经济性主要归功于串联甲酰基化-巴豆基甲硅烷基化/Tamao氧化-非对映选择性互变异构反应的应用，该反应在一步中实现了通常需要大量多步序列的目标。
• Tandem Silylformylation−Crotylsilylation/Tamao Oxidation of Internal Alkynes: A Remarkable Example of Generating Complexity from Simplicity
  作者：Jared T. Spletstoser、Michael J. Zacuto、James L. Leighton

  DOI：10.1021/ol802489w

  日期：2008.12.18

  The rhodium-catalyzed tandem silylformylation-crotylsilylation reaction has been extended to include internal alkynes. Tamao oxidation of the initial product leads to the production of a substituted enol, which undergoes highly diastereoselective tautomerization. The resulting one-pot procedure fashions three new stereocenters, a ketone, and a terminal alkene from a butenyl group, a propynyl group

  铑催化的串联甲硅烷基甲酰化-巴豆基甲硅烷基化反应已扩展到包括内部炔烃。初始产物的 Tamao 氧化导致取代的烯醇的产生，该烯醇经历高度非对映选择性互变异构化。由此产生的一锅法由丁烯基、丙炔基、甲硅烷基氢化物、H2O2 和 CO 形成三个新的立体中心、一个酮和一个末端烯烃。