meso-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol | 1039753-27-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: meso-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol
• CAS: 1039753-27-9
• 化学式: C₁₄H₂₆O₂Si₂
• 分子量: 282.53
• InChiKey: SCVHESYWMCOFFK-OKILXGFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.25
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  meso-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol 在 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 以94%的产率得到meso-3,4-dimethyl-hexa-1,5-diyne-3,4-diol
  参考文献：
  名称：

  Ethynylbenzenoid metabolites of Antrodia camphorata: synthesis and inhibition of TNF expression

  摘要：

  Antrocamphin A和B，以及（±）-epi-antrodioxolanone已经从一个共同的前体合成。Antrocamphin A显示抗炎活性，但也具有细胞毒性。

  DOI：

  10.1039/c3ob42333f
• 作为产物：
  描述：

  2,3-丁二酮 、 三甲基乙炔基硅 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以33%的产率得到meso-3,4-dimethyl-1,6-bis(trimethylsilyl)hexa-1,5-diyne-3,4-diol
  参考文献：
  名称：

  In Search of Efficient 5-Endo-dig Cyclization of a Carbon-Centered Radical: 40 Years from a Prediction to Another Success for the Baldwin Rules

  摘要：

  Despite being predicted to be stereoelectronically favorable by the Baldwin rules, efficient formation of a C-C bond through a 5-endo-dig radical cyclization remained unknown for more than 40 years. This work reports a remarkable increase in the efficiency of this process upon beta-Ts substitution, which led to the development of an expedient approach to densely functionalized cyclic 1,3-dienes. Good qualitative agreement between the increased efficiency and stereoselectivity for the 5-endo-dig cyclization of Ts-substituted vinyl radicals and the results of density functional theory analysis further confirms the utility of computational methods in the design of new radical processes. Although reactions of Br atoms generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side products, the yields of target bromosulfones in the photochemically induced reactions can be increased by recycling the dibromide byproduct into the target bromosulfones through a sequence of addition/elimination reactions at the exocyclic double bond. Discovery of a relatively efficient radical 5-endo-dig closure, accompanied by a C-C bond formation, provides further support to stereoelectronic considerations at the heart of the Baldwin rules and fills one of the last remaining gaps in the arsenal of radical cyclizations.

  DOI：

  10.1021/ja801478n

文献信息

• Controlled Cyclopolymerization of 1,5-Hexadiynes to Give Narrow Band Gap Conjugated Polyacetylenes Containing Highly Strained Cyclobutenes
  作者：Cheol Kang、Kijung Jung、Sojeong Ahn、Tae-Lim Choi

  DOI：10.1021/jacs.0c07666

  日期：2020.10.7

  decades, cyclopolymerization of α,ω-diyne derivatives has been an effective method to synthesize various soluble polyacetylenes containing five- to seven-membered rings in the backbone. However, cyclopolymerization to form four-membered carbocycles was considered impossible due to their exceptionally high ring strain (∼30 kcal/mol). Herein, we demonstrate the successful cyclopolymerization of rationally

  几十年来，α,ω-二炔衍生物的环聚合一直是合成主链中含有五至七元环的各种可溶性聚乙炔的有效方法。然而，环聚合形成四元碳环被认为是不可能的，因为它们具有极高的环应变（~30 kcal/mol）。在此，我们展示了合理设计的 1,5-己二炔衍生物的成功环聚合，以提供在每个重复单元中含有高应变环丁烯的各种聚乙炔。经过筛选，含有庞大的二异丙基苯基的 Ru 催化剂有效地促进了具有挑战性的四元环环化，从而能够以可控的方式合成高分子量（高达 40 kDa）的聚乙炔。此外，活性聚合允许通过与开环易位聚合以及两种不同的 1,5-己二炔单体的嵌段共聚相结合来合成嵌段共聚物，从而得到完全共轭的聚乙炔。这些新聚合物出人意料地显示出比传统取代聚乙炔窄得多的带隙 > 0.2 eV。有趣的是，计算研究表明，含有环丁烯的共轭主链中键长的变化要小得多，导致沿聚合物链的高度离域的 π 电子和较低的带隙。这些新聚合物出人意料地显示出比传统取代聚乙炔更窄的带隙