(E)-2-methylpent-2-en-4-yn-1-ol | 53768-02-8

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: (E)-2-methylpent-2-en-4-yn-1-ol
• 英文别名: (E)-2-methyl-2-en-4-yne-1-ol；(E)-2-methyl-pent-2-en-4-yn-1-ol
• CAS: 53768-02-8
• 化学式: C₆H₈O
• 分子量: 96.1289
• InChiKey: CXJQXXUKVILMQO-GQCTYLIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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-methylpent-2-en-4-yn-1-ol 在 bis(triphenylphosphine)palladium(II)-chloride copper(l) iodide 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.5h， 生成 (E)-6-[5-(tert-butyldimethylsilyloxy)-4-methyl-3-penten-1-yn-1-yl]-1H-purine
  参考文献：
  名称：

  Synthesis of 6-alkenyl- and 6-alkynylpurines with cytokinin activity

  摘要：

  DOI：

  10.1016/s0040-4020(98)01027-8
• 作为产物：
  描述：

  (E)-2-methyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol 在 甲醇 、 potassium carbonate 作用下， 以78%的产率得到(E)-2-methylpent-2-en-4-yn-1-ol
  参考文献：
  名称：

  分子内吡啶酮/烯炔光环加成：[4 + 4]和[2 + 2]途径的划分

  摘要：

  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。

  DOI：

  10.1021/ol200390j

文献信息

• Accessible triplet excited states in the photoisomerization of allenes with extended conjugation
  作者：Jonathan Álvarez-García、Ramón García-Lago、José Lorenzo Alonso-Gómez、Carlos Silva López、María Magdalena Cid

  DOI：10.1039/d1dt03688b

  日期：——

  complexes exhibit facile isomerization of the conjugated double bonds upon ambient light exposure. Simulations unveiled a very efficient intersystem crossing and the consequent key role of the triplet states in the observed photochemistry of these substrates upon rhenium(I) complexation.

  已经合成了一系列含二齿丙二烯和烯炔的配体，并研究了它们的铼( I )配合物的光化学性质。这些配合物在环境光照射下表现出共轭双键的容易异构化。模拟揭示了一种非常有效的系间交叉，以及三重态在铼 ( I ) 络合时观察到的这些底物的光化学中的关键作用。
• Studies directed toward the total synthesis of tetronolide 1. An enantioselective synthesis of the octahydronaphthalene unit
  作者：Robert K. Boeckman、Thomas E. Barta、Scott G. Nelson

  DOI：10.1016/s0040-4039(00)79871-6

  日期：1991.8

  An efficient enantioselective route to the octahydronaphthalene unit present in tetronolide (1), the stereochemically complex aglycone common to the tetrocarcins, a novel group of antitumor substances, is described. The sequence employs the intramolecular Diels-Alder reaction to control the relative stereochemistry present on the trans decalin ring system, and incorporates a masked acylating agent

  到八氢化单元本高效的对映选择性路线tetronolide（1），其立体化学复杂苷元共同的tetrocarcins，一组新的抗肿瘤物质，进行说明。该序列利用分子内Diels-Alder反应控制存在于反式十氢化萘环系统上的相对立体化学，并结合了一种掩蔽的酰化剂，该掩蔽的酰化剂应允许两个关键片段2和3偶联，如戊烯4与甲醇和甲醇的反应所证明的那样。模型α-羟基酯。
• 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。
• Bohlmann,F.; Bax,H.-J., Chemische Berichte, 1974, vol. 107, p. 1773 - 1776
  作者：Bohlmann,F.、Bax,H.-J.

  DOI：——

  日期：——
• 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.