(E)-2-methyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol | 165604-92-2

• 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)-2-methyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol
• 英文别名: (E)-2-methyl-5-trimethylsilylpent-2-en-4-yn-1-ol
• CAS: 165604-92-2
• 化学式: C₉H₁₆OSi
• 分子量: 168.311
• InChiKey: UXFMANKKIRECPN-RMKNXTFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.81
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2-methyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol 在 甲醇 、 manganese(IV) oxide 、 copper(l) iodide 、 四(三苯基膦)钯 、 正丁基锂 、 TMS-quinidine 、 碘 、 sodium methylate 、 lithium perchlorate 、 copper(l) cyanide 、 二异丙胺 、 N,N-二异丙基乙胺 、 cesium fluoride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 56.67h， 生成 methyl (R,4E,6E,8E)-3-hydroxy-2,2,4-trimethyl-10-(oxazol-5-yl)deca-4,6,8-trienoate
  参考文献：
  名称：

  Inthomycins A，B和C的有机催化不对称合成†

  摘要：

  分离自链霉菌属的恶唑三烯类抗生素-（+）-ththomycin A，（+）-ththomycin B和（-）-ththomycin C的总合成是通过C1的高度对映体和立体选择性构建而完成的利用金鸡纳生物碱催化的不对称β-内酯合成及其无异构化的Stille偶联，可合成–C7（碘二烯基）醛醇单元（E）-5-（3-（三丁基锡烷基）烯丙基）恶唑。

  DOI：

  10.1039/c2ob26084k
• 作为产物：
  描述：

  3-碘-2-甲基丙-2-烯-1-醇 、 三甲基乙炔基硅 在 四氢吡咯 、 copper(l) iodide 、 四(三苯基膦)钯 作用下， 反应 2.0h， 以80%的产率得到(E)-2-methyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol
  参考文献：
  名称：

  Elansolid生物合成的分子基础：前所未有的醌型甲基巯基引发的分子内Diels-Alder Cycloaddition / Macroactonization的证据

  摘要：

  完全控制：通过饲喂实验，生物合成基因簇的分析以及模型底物的合成，阐明了滑翔细菌Chitinophaga sancti合成的一种新的，结构独特的聚酮化合物代谢物elansolide A1的生物合成的关键步骤。这些步骤包括前所未有的脱水反应，分子内Diels-Alder环加成反应（IMDA）和不寻常的大内酯化作用。

  DOI：

  10.1002/anie.201006880

文献信息

• Intramolecular Pyridone/Enyne Photocycloaddition: Partitioning of the [4 + 4] and [2 + 2] Pathways
  作者：Svitlana Kulyk、William G. Dougherty、W. Scott Kassel、Michael J. Zdilla、Scott McN. Sieburth

  DOI：10.1021/ol200390j

  日期：2011.5.6

  Intramolecular photocycloaddition (>290 nm) between a 1,3-enyne and a 2-pyridone is far more selective than the intermolecular version; a three-atom linkage both controls regiochemistry and separates the [2 + 2] and [4 + 4] pathways. All four head-to-head, head-to-tail, tail-to-head, and tail-to-tail tetherings have been investigated. Linkage via the ene of the enyne leads to [2 + 2] products regardless

  1,3-烯炔和2-吡啶酮之间的分子内光环加成（> 290 nm）比分子间形式具有更高的选择性。三原子链接既控制区域化学作用，又分离[2 + 2]和[4 + 4]途径。已对所有四个头对头，头对尾，尾对头和尾对尾的系链进行了研究。连杆经由所述烯炔引线的烯[2 + 2]的产品，无论烯烃的几何形状，而连杆通过在[4 + 4]的cycloadducts炔结果。[4 + 4]环加成反应的桥联1,2,5-环辛三烯产物不稳定，并会随后发生[2 + 2]二聚反应。
• Total Synthesis of (+)-Tubelactomicin A. 1. Stereoselective Synthesis of the Lower-Half Segment by an Intramolecular Diels−Alder Approach
  作者：Toru Motozaki、Kiyoto Sawamura、Akari Suzuki、Keigo Yoshida、Tatsuo Ueki、Aiko Ohara、Ryosuke Munakata、Ken-ichi Takao、Kin-ichi Tadano

  DOI：10.1021/ol0507625

  日期：2005.5.1

  [reaction: see text]. Starting from diethyl (R)-malate, synthesis of the lower-half segment of (+)-tubelactomicin A, a 16-membered macrolide antibiotic, has been achieved. The synthesis involved the highly endo- and pi-facial selective intramolecular Diels-Alder reaction achieved using a trisubstituted methacrolein derivative tethering a 10-carbon dienyne unit at the beta-carbon, which in turn was

  [反应：请参见文字]。从（R）苹果酸二乙酯开始，已经合成了一种由16元大环内酯类抗生素组成的（+）-tubelactomicin A的下半部分。该合成涉及高度内切和表面选择性的分子内Diels-Alder反应，该反应是通过在β-碳上束缚10碳二烯单元的三取代的甲基丙烯醛衍生物实现的，而后者又由已知的烯丙基化苹果酸衍生物制得。
• Formation and isomerization of polycyclic 1,5-enynes
  作者：Paul B. Finn、Svitlana Kulyk、Scott McN. Sieburth

  DOI：10.1016/j.tetlet.2015.01.145

  日期：2015.6

  A 1,5-enyne with the alkyne flanked by a cyclopropane and a cyclobutane, formed by intramolecular [2+2] photocycloaddition of a pyridone with an enyne, undergoes gold catalyzed ring closure to give a cyclopentene, without isomerization of either small ring. The ring closure can also be effected by thiol radical conditions. The chemistry of the resulting tetracycle with its five stereogenic centers

  由吡啶酮与烯炔的分子内[2 + 2]光环加成反应形成的带有炔烃的1,5-烯炔与侧接环丙烷和环丁烷的环戊烯进行金催化的闭环反应生成环戊烯，而没有任何小环的异构化。闭环也可以通过巯基条件进行。已经研究了所得到的四环化合物及其五个立体异构中心的化学性质。
• Synthesis of 6-alkenyl- and 6-alkynylpurines with cytokinin activity
  作者：Anders Bråthe、Lise-Lotte Gundersen、Frode Rise、Aud Berglen Eriksen、Ane V. Vollsnes、Linea Wang

  DOI：10.1016/s0040-4020(98)01027-8

  日期：1999.1
• Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs
  作者：Angel R. de Lera、Beatriz Iglesias、Jesus Rodriguez、Rosana Alvarez、Susana Lopez、Xavier Villanueva、Esteve Padros

  DOI：10.1021/ja00136a021

  日期：1995.8

  Four positional isomers of trans-retinal (1) differing in the location of the side-chain methyl groups have been prepared by a combination of Wittig and highly stereocontrolled Suzuki coupling reactions. The incubation of 9-demethyl-10-methylretinal (5) with bacterioopsin yielded an artificial pigment with an opsin shift of 4630 cm(-1) The other three analogs, namely 13-demethyl-14-methylretinal (3), 13-demethyl-12-methylretinal (4), and 9-demethyl-8-methylretinal (6) did not bind to the apoprotein. In order to rationally address the intrinsic structural differences among analogs which could be relevant to the discrimination exhibited by the protein binding site, ab initio calculations with complete optimization at the 3-21G level were performed on model N-methylretinal iminium salts derived from aldehydes 1 and 3-6. The validity of the approach was inferred from the remarkable coincidence between the minimized structure of N-methylretinal Schiff base (PSB-1) and the structural parameters displayed by N-methyl-N-phenylretinal iminium perchlorate (38b). Computations clearly show that the location of the methyl groups on the polyene side chain is of the utmost importance in determining the overall shape of the retinal ligands. Those structural effects, added to the dominant steric and electronic restrictions of the binding pocket, would explain the observed discrimination among the analogs 3-6, with minor structural changes, and perhaps among other retinals reported in the literature. Additionally, the theoretical and experimental results obtained with 9-demethyl-8-methylretinal (6) provide further indirect evidence of the importance of the 6-s-trans conformation for the native chromophore in bacteriorhodopsin.