(E)-tert-butyl((3-iodobut-2-en-1-yl)oxy)diphenylsilane | 473758-72-4

• 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)-tert-butyl((3-iodobut-2-en-1-yl)oxy)diphenylsilane
• 英文别名: (E)-tert-butyl(3-iodobut-2-enyloxy)diphenylsilane；tert-butyl-[(E)-3-iodobut-2-enoxy]-diphenylsilane
• CAS: 473758-72-4
• 化学式: C₂₀H₂₅IOSi
• 分子量: 436.408
• InChiKey: FYQPBXMYUNXGFE-BMRADRMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  (E)-tert-butyl((3-iodobut-2-en-1-yl)oxy)diphenylsilane 在 四(三苯基膦)钯 copper(l) iodide 、 copper diacetate 、 silver nitrate 、 异丙胺 、 锌 作用下， 以 甲醇 、 水 为溶剂， 反应 26.0h， 生成 (1R)-4-[(1E,3E,5Z,7E)-9-[tert-butyl(diphenyl)silyl]oxy-3,7-dimethylnona-1,3,5,7-tetraenyl]-3,5,5-trimethylcyclohex-3-en-1-ol
  参考文献：
  名称：

  Synthesis of biotinylated retinoids for cross-linking and isolation of retinol binding proteins

  摘要：

  The synthesis of (3R)-3-[Boc-Lys(biotinyl)-O]-11-cis-retinol bromoacetate and 3-[Boc-Lys(biotinyl)-0]-all trans-retinol chloroacetate is described. These biotinylated retinoids a-re instrumental in labeling the retinol binding proteins (RBPs) via a nucleophilic displacement of the haloacetate by a residue in the binding site of the protein. The covalently linked biotin will allow for a facile isolation and purification of the protein on a streptavidin column thus rendering the protein ready for a tryptic digest followed by mass spectrometric analysis. The 11-cis retinoid was synthesized via metal reduction of an alkyne intermediate generated from a Homer-Wadsworth-Emmons (HWE) reaction whereas the all-trans was synthesized via two consecutive HWE couplings. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00667-1
• 作为产物：
  描述：

  3-碘-丁-2-烯-1-醇 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以93%的产率得到(E)-tert-butyl((3-iodobut-2-en-1-yl)oxy)diphenylsilane
  参考文献：
  名称：

  Total Synthesis of Brevisamide

  摘要：

  A convergent synthesis of brevisamide (1) is described based on the application of the crotyl silane-based [4 + 2]-annulation used for the preparation of the advanced oxygenated tetrahydropyran intermediate 2. The side chain bearing a conjugated (E,E)-diene was efficiently constructed under modified Negishi cross-coupling conditions.

  DOI：

  10.1021/ol901801h

文献信息

• Exploiting the Pd- and Ru-Catalyzed Cycloisomerizations:  Enantioselective Total Synthesis of (+)-Allocyathin B₂
  作者：Barry M. Trost、Li Dong、Gretchen M. Schroeder

  DOI：10.1021/ja051547m

  日期：2005.7.1

  Pd- and Ru-catalyzed cycloisomerizations of 1,6-enynes are compared and contrasted. Such considerations led to the enantioselective synthesis of a cyathin terpenoid, (+)-allocyathin B(2) (1). The synthesis features a Pd-catalyzed asymmetric allylic alkylation (AAA) to install the initial quaternary center, a Ru-catalyzed diastereoselective cycloisomerization to construct the six-membered ring, and

  比较和对比了 Pd 和 Ru 催化的 1,6-烯炔的环异构化。这样的考虑导致了 cyathin 萜类化合物 (+)-allocyathin B(2) (1) 的对映选择性合成。该合成具有 Pd 催化的不对称烯丙基烷基化 (AAA) 以安装初始季中心，Ru 催化的非对映选择性环异构化以构建六元环，以及非对映选择性羟基化 Knoevenagel 反应以引入最终的羟基。我们首次证明了 Pd 和 Ru 催化的环异构化反应中基于机制的立体化学发散，以及用带有碳烷氧基的炔烃创建烯烃几何形状。对这些观察结果提出了机械合理化。
• On the Bioactive Conformation of the Rhodopsin Chromophore: Absolute Sense of Twist around the 6-s-cis Bond
  作者：Yukari Fujimoto、Jun Ishihara、Shojiro Maki、Naoko Fujioka、Tao Wang、Takumi Furuta、Nathan Fishkin、Babak Borhan、Nina Berova、Koji Nakanishi

  DOI：10.1002/1521-3765(20011001)7:19<4198::aid-chem4198>3.0.co;2-x

  日期：2001.10.1

  carrying the ring moiety. The GTP-binding assay of pigment Rh-(2a), incorporating retinal analogue 2a, has shown that its activity is 80% that of the native pigment. That is, the overall conformation around the 6-s bond is retained in the steps leading to G-protein activation.

  将视蛋白与合成的6-s锁定类视色素2a和2b一起孵育只会导致由α锁定的2a形成色素，其CD光谱与天然视紫红质（Rh）相似。这表明视紫红质中发色团的6-s键为顺式，且其螺旋度为负。较早的交联研究表明，在batho-Rh到lumi-Rh的转化中发生的11-顺式到全反式光异构化引起了带有环部分的一侧的翻转。结合视网膜类似物2a的色素Rh-（2a）的GTP结合测定表明，其活性是天然色素的80％。即，在导致G蛋白活化的步骤中保留了6-s键周围的整体构象。
• Total syntheses of <i>ent</i>-hypocoprin A and <i>ent</i>-hypocoprin B
  作者：Koichiro Ota、Taiki Watanabe、Shuntaro Igarashi、Shinnosuke Okazaki、Kazuo Kamaike、Hiroaki Miyaoka

  DOI：10.1039/d2ra02891c

  日期：——

  bicyclic skeletal sesquiterpenoids, namely, hypocoprin A and hypocoprin B. The synthesis involved conjugate addition accelerated by trimethylsilyl chloride, construction of the ten-membered ring via the intramolecular SN2 reaction promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene, and osmium-mediated π-facial selective dihydroxylation to functionalize the 1,1-disubstituted alkene.

  本研究报告了独特的 3/10 双环骨架倍半萜类化合物的对映体，即次菌素 A 和次菌素 B 的立体选择性全合成。合成涉及三甲基氯硅烷加速的共轭加成，通过分子内 S N构建十元环1,8-二氮杂双环[5.4.0]十一碳-7-烯促进的2反应，以及锇介导的π-面选择性二羟基化以官能化1,1-二取代烯烃。
• Total Synthesis of (+)-Thiazinotrienomycin E
  作者：Amos B. Smith、Zehong Wan

  DOI：10.1021/ol991049g

  日期：1999.11.1

  [GRAPHICS]The first total synthesis of (+)-thiazinotrienomycin E (1), member of a novel class of cytotoxic ansamycin antibiotics, has been achieved. The synthesis features a highly efficient construction of the aromatic fragment 3 incorporating TBS protection of the aniline, a significantly improved synthesis of (-)-19, an intermediate employed in our trienomycins A and F total syntheses, application of the Kocienski modified Julia protocol to elaborate the E,E,E-triene subunit, an efficient union of 3 and (+)-4, and Mukaiyama macrolactamization to access the thiazinotrienomycin macrolide.
• Total Synthesis of (+)-Allocyathin B₂
  作者：Barry M. Trost、Li Dong、Gretchen M. Schroeder

  DOI：10.1021/ja0435586

  日期：2005.3.9

  The first enantioselective synthesis of (+)-allocyathin was achieved. The synthesis features a Pd-catalyzed asymmetric allylic alkylation to install the first quaternary center, a Ru-catalyzed diastereoselective cycloisomerization to construct the six-membered ring, and a diastereoselective hydroxylative Knoevenagel reaction to introduce the final hydroxyl group. The unusual olefin isomerization of the Ru-catalyzed cycloisomerization was discussed and exploited for the synthesis.