(E)-(tert-butyl)(4-iodo-3-methylbut-3-enyloxy)diphenylsilane | 148583-99-7

• 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: (E)-(tert-butyl)(4-iodo-3-methylbut-3-enyloxy)diphenylsilane
• 英文别名: (E)-4-(tert-butyldiphenylsilyloxy)-1-iodo-2-methyl-1-butene；tert-butyl-(4-iodo-3-methyl-but-3-enyloxy)-diphenyl-silane；(E) 1-(t-butyldiphenylsiloxy)-4-iodo-3-methyl-3-butene；tert-butyl-[(E)-4-iodo-3-methylbut-3-enoxy]-diphenylsilane
• CAS: 148583-99-7
• 化学式: C₂₁H₂₇IOSi
• 分子量: 450.435
• InChiKey: WMCLIIIEEOGITJ-ISLYRVAYSA-N

物化性质

• 沸点：
  425.5±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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)(4-iodo-3-methylbut-3-enyloxy)diphenylsilane 在 copper(l) iodide 、 四(三苯基膦)钯 、 四丁基氟化铵 、 potassium carbonate 、 溶剂黄146 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 24.17h， 生成 N-{(R*)-[(1R*,2S*,1'R*,2'S*)-2'-(2-hydroxyethyl)-2'-methylbicyclopropyl-2-yl]phenylmethyl}-P,P-diphenylphosphonamide
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 在 4-二甲氨基吡啶 、 zirconocene dichloride 、 碘 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.25h， 生成 (E)-(tert-butyl)(4-iodo-3-methylbut-3-enyloxy)diphenylsilane
  参考文献：
  名称：

  Synthesis of an advanced forskolin intermediate

  摘要：

  The 8,13-epoxylabdane derivative rac-19 was prepared in eight steps commencing from (E,E)-farnesol (8). Key reactions are the formation of 7 from drimenal (9b) and 6, Sharpless I epoxidation (7 --> 11), epoxy alcohol oxidation (11 --> 16), reductive epoxide cleavage (16 --> 15), peracid epoxidation (15 --> 18), and the trimethylsilyl triflate-mediated conversion of 18 into 19.

  DOI：

  10.1016/s0040-4020(01)86324-9

文献信息

• An Oxidative [2,3]-Sigmatropic Rearrangement of Allylic Hydrazides
  作者：Benjamin F. Strick、Devon A. Mundal、Regan J. Thomson

  DOI：10.1021/ja2066219

  日期：2011.9.14

  The development of an efficient oxidative [2,3]-sigmatropic rearrangement of allylic hydrazides, via singlet N-nitrene intermediates, is reported. The requisite allylic hydrazide precursors are readily prepared and undergo smooth sigmatropic rearrangement upon exposure to iodosobenzene. The products of this novel transformation are shown to be useful precursors to a variety of compounds.

  据报道，通过单线态 N-硝烯中间体开发了烯丙基酰肼的有效氧化 [2,3]-sigmatropic 重排。必需的烯丙基酰肼前体很容易制备，并在暴露于碘代苯后进行平滑的σ重排。这种新转化的产物被证明是各种化合物的有用前体。
• Stereochemical Study of a Transannular Michael Reaction Cascade
  作者：Haoran Xue、Peddabuddi Gopal、Jiong Yang

  DOI：10.1021/jo301287z

  日期：2012.10.19

  systematically explored a transannular Michael reaction cascade for stereoselective synthesis of polycyclic systems. Both E,Z- and E,E-1,7-bis-enones in the form of 14-membered macrocyclic lactones underwent transannular cyclization to give polycyclic products with high efficiency and excellent diastereoselectivity. In contrast, Z,E- and Z,Z-macrocyclic lactones did not cyclize under similar reaction

  我们系统地探索了多环系统的立体选择性合成的跨环迈克尔反应级联。两个E，Z -和E，E -1,7-双-烯酮的形式14元大环内酯类后行跨环的环化，得到的多环产品具有高效率和优异的非对映选择性。相反，Z，E-和Z，Z-大环内酯在相似的反应条件下不环化。我们的研究揭示了这种环过环化过程与环过Diels-Alder反应之间的相似性和微妙的立体化学差异。为了有效合成大环内酯，开发了一种酰基烯酮方法。这项研究还阐明了通过分子内Reformatsky反应制备大环内酯的大环化的范围和局限性。
• Diastereoselective Additions of Chiral Vinylzinc Reagents to α-Chiral Aldehydes
  作者：James A. Marshall、Patrick Eidam

  DOI：10.1021/ol0363568

  日期：2004.2.1

  [reaction: see text] Additions of vinylic zinc bromide reagents to alpha-chiral aldehydes (R(1) = CH(2)OTBS, R(2) = Me; R(1) = Me, R(2) = OTBS) in the presence of lithiated (+)- or (-)-N-methylephedrine proceed with predominant reagent control to afford anti or syn adducts stereoselectively, except when the aldehydes possess an alkoxy substituent at the alpha- or beta-positions (R(1) = Me, R(2) = OBn;

  [反应：请参见文本]将乙烯基溴化锌试剂添加到α-手性醛中（R（1）= CH（2）OTBS，R（2）= Me； R（1）= Me，R（2）= OTBS）在锂化（+）-或（-）-N-甲基麻黄碱的存在下，进行主要试剂控制以立体选择性地提供抗加成或顺加成，除非醛在α-或β-位置具有烷氧基取代基（R（1 ）= Me，R（2）= OBn; R（1）= CH（2）OBn，R（2）= Me），在这种情况下，螯合控制的加合物占主导地位。
• Asymmetric Total Synthesis of (−)-Phaeocaulisin A
  作者：Áron Péter、Giacomo E. M. Crisenza、David J. Procter

  DOI：10.1021/jacs.2c02188

  日期：2022.4.27

  tetracyclic framework. Prompted by the promising biological profile of phaeocaulisin A and by the absence of a synthetic route for its provision, we have implemented the first enantioselective total synthesis of phaeocaulisin A in 17 steps with 2% overall yield. Our route design builds on the identification of an enantioenriched lactone intermediate, tailored with both a ketone moiety and a conjugated

  姜黄（姜和姜黄家族）的治疗特性在传统医学中早已为人所知。然而，直到最近才有从姜黄中提取的愈创木脂类倍半萜已提交生物测试，并强调其增强的生物活性。在这些化合物中，phaeocaulisin A 显示出显着的抗炎和抗癌活性，这似乎与嵌入其四环框架中的独特桥接缩醛部分有关。由于 phaeocaulisin A 的有希望的生物学特征以及缺乏合成路线的提示，我们已经在 17 个步骤中实现了 phaeocaulisin A 的第一个对映选择性全合成，总产率为 2%。我们的路线设计建立在鉴定富含对映体的内酯中间体的基础上，该中间体采用酮部分和共轭烯烃系统进行定制。利用原型单电子转移 (SET) 还原剂二碘化钐 (SmI) 实现的 umpolung 羰基-烯烃偶联反应性2), the lactone intermediate was submitted to two sequential SmI2-mediated
• Synthetic studies of pestalotiopsin A: asymmetric synthesis of the 2-oxabicyclo[3.2.0]heptane substructure
  作者：Ken-ichi Takao、Hiroshi Saegusa、Tomohiro Tsujita、Takenori Washizawa、Kin-ichi Tadano

  DOI：10.1016/j.tetlet.2005.06.133

  日期：2005.8

  A functionalized 2-oxabicyclo [3.2.0]heptan-3-one derivative, possessing all the skeletal carbons of pestalotiopsin A, has been synthesized. For the preparation of intermediary cyclobutane derivatives in enantioenriched form, the Lewis acid-catalyzed [2+2] cycloaddition of N-propiolated Oppoizer's camphorsultam with dimethylketene bis(trimethylsilyl) acetal followed by a stereo-selective 1,4-hydride addition/protonation, has been developed. (c) 2005 Elsevier Ltd. All rights reserved.