(E)-1-t-butyldimethylsilyloxy-3-tributylstannylbut-2-ene | 160537-79-1

• 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: (E)-1-t-butyldimethylsilyloxy-3-tributylstannylbut-2-ene
• 英文别名: (E)-tert-butyldimethyl[3-(tributylstannyl)but-2-enyloxy]silane；tert-butyl-dimethyl-[(E)-3-tributylstannylbut-2-enoxy]silane
• CAS: 160537-79-1
• 化学式: C₂₂H₄₈OSiSn
• 分子量: 475.418
• InChiKey: PLEVQVMUANPHAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.34
• 重原子数：
  25.0
• 可旋转键数：
  13.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E)-1-t-butyldimethylsilyloxy-3-tributylstannylbut-2-ene 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Transannular Diels-Alder route to systems related to dynemicin A

  摘要：

  DOI：

  10.1021/ja00176a060
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (2E)-3-methyl-3-tributylstannylprop-2-en-1-ol 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到(E)-1-t-butyldimethylsilyloxy-3-tributylstannylbut-2-ene
  参考文献：
  名称：

  Stereocontrolled Synthesis of (11Z)-Retinal and Its Analogues

  摘要：

  Suzuki coupling of stereochemically pure (Z)-bromotetraene 1-which is extremely unstable but can be kept in frozen benzene in the presence of a small amount of PPh3 at &sminus 01;20°C-and (Z)-alkenylboronic acid 2 provides the stereocontrolled synthesis of (11Z)-retinal 3. The 11Z configuration, which is introduced by selective catalytic debromination of the corresponding dibromo precursor of 1, is retained in this step. TBDMS = tBuMe2 Si.

  DOI：

  10.1002/(sici)1521-3773(19980216)37:3<320::aid-anie320>3.0.co;2-4

文献信息

• Total synthesis and absolute configuration of koshikalide
  作者：Kazuki Kunifuda、Arihiro Iwasaki、Masashi Nagamoto、Kiyotake Suenaga

  DOI：10.1016/j.tetlet.2016.06.002

  日期：2016.7

  koshikalide, a 14-membered macrolide that contains three olefins, was achieved. The skipped diene in the cyclic system was efficiently constructed by very mild Stille coupling at low temperature. The absolute stereochemistry was established by comparison of the specific optical rotations of natural and synthesized koshikalide.

  首次实现了全合成碱的合成，这是一种含有三种烯烃的14元大环内酯。通过在低温下进行非常温和的Stille偶联，可以有效地构建循环系统中跳过的二烯。通过比较天然和合成的koshikalide的特定旋光性，可以建立绝对立体化学。
• Asymmetric Construction of the Azaspiro[5.5]undec-8-ene System Towards Gymnodimine Synthesis
  作者：Takashi Tsujimoto、Jun Ishihara、Mariko Horie、Akio Murai

  DOI：10.1055/s-2002-20450

  日期：——

  In the course of the synthetic studies on gymnodimine, a potent shellfish toxin, the asymmetric construction of the azaspirocyclic part was achieved by the (-)-siam·Cu(SbF6)2 complex catalyzed intermolecular Diels-Alder reaction in high exo- and enantioselectivities.

  在对 Gymnodimine 这种强效贝类毒素的综合研究过程中，通过（-）-siam·Cu（SbF6）2 配合物催化的具有高外向选择性和对映选择性的分子间 Diels-Alder 反应，成功实现了氮杂螺环部分的不对称构建。
• Total Synthesis of (−)-Zampanolide and Questionable Existence of (−)-Dactylolide as the Elusive Biosynthetic Precursor of (−)-Zampanolide in an Okinawan Sponge
  作者：Jun’ichi Uenishi、Takuya Iwamoto、Junichi Tanaka

  DOI：10.1021/ol901167g

  日期：2009.8.6

  concise total synthesis of (−)-zampanolide, (−)-1, and (−)-dactylolide, (−)-2, is described. Synthetic highlights include (i) a mild Horner-Wadsworth-Emmons reaction providing the seco acid, (ii) an unusual stepwise cross-coupling reaction of a 1,1-dibromodiene with inversion of olefin geometry, and (iii) specific O-Michael reaction conditions using catalytic LHMDS with TMEDA for the synthesis of functionalized

  描述了一种新的简明的全合成的（-）-樟脑内酯（-）-1和（-）-癸内酯（-）-2。合成亮点包括（i）温和的Horner-Wadsworth-Emmons反应提供癸二酸；（ii）1,1-二溴二烯的不寻常逐步交叉偶联反应，且烯烃的几何结构反转；以及（iii）特定的O- Michael反应条件，使用催化LHMDS和TMEDA合成功能化的2,6-顺式-四氢吡喃。分析了海用海绵提取物中是否存在（-）-2作为（-）-扎曼醇化物的生物合成前体。
• Studies on the Mechanism of B(C₆F₅)₃-Catalyzed Hydrostannylation of Propargylic Alcohol Derivatives
  作者：Martins S. Oderinde、Michael G. Organ

  DOI：10.1002/anie.201204060

  日期：2012.9.24

  Sleight of hydride: B(C6F5)3 catalyzes the hydrostannylation of propargylic alcohols in a regio‐ and stereoselective manner (see scheme). This Lewis acid first abstracts a hydride from the stannane, thus forming a borohydride/stannyl cation pair, the stability of which depends on solvent and ligands. Deuterium‐labeling experiments showed that the source that delivers a hydride to the alkenyl cation

  氢化物的轻度：B（C 6 F 5）3以区域和立体选择性的方式催化炔丙醇的加氢甲锡化反应（参见方案）。该路易斯酸首先从锡烷中提取氢化物，从而形成硼氢化物/锡烷基阳离子对，其稳定性取决于溶剂和配体。氘标记实验表明，将氢化物传递至烯基阳离子的来源不是硼氢化物，而是锡烷的第二分子。
• Total Synthesis of (-)-Austalide B. A Generic Solution to Elaboration of the Pyran/p-Cresol/Butenolide Triad
  作者：Leo A. Paquette、Ting-Zhong Wang、Matthew R. Sivik

  DOI：10.1021/ja00104a012

  日期：1994.12

  The toxic meroterpenoid (-)-austalide B has been prepared in its natural form by chemical modification of the readily available optically active enedione 11. Following stereocontrolled Robinson annulation to give 13 and fully regiocontrolled gem-dimethylation of this intermediate, the highly functionalized tetracyclic ortho ester 22 was produced in four additional steps. At this point, it proved an easy matter to obtain 23 by Baeyer-Villiger oxidation. For the purpose of annealing rings E and F, carbomethoxy trinate 41 was prepared and coupled to 42 through the agency of Pd-2(dba)(3) and (furyl)(3)P. With arrival at 39, it proved possible by sequential intramolecular Claisen condensation, O-methylation, and modest warming to produce 50. Deprotection of the secondary hydroxyl and inversion of its configuration delivered synthetic austalide B, which exhibited melting point, specific rotation, infrared, and NMR properties (H-1 and C-13) identical to the natural material obtained from South Africa.