octa-4t,6t-dien-1-yn-3-ol | 135958-18-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: octa-4t,6t-dien-1-yn-3-ol
• 英文别名: (4E,6E)-octa-4,6-dien-1-yn-3-ol；octa-4t,6t-dien-1-yn-3-ol；Octa-4t,6t-dien-1-in-3-ol
• CAS: 135958-18-8
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: RLLKIJNPVVBTQZ-TWTPFVCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.11
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  octa-4t,6t-dien-1-yn-3-ol 在 四氢呋喃 、 lithium aluminium tetrahydride 、 乙基溴化镁 作用下， 生成 hexadeca-2ξ,4ξ,6ξ,8ξ,10ξ,12ξ,14ξ-heptaene
  参考文献：
  名称：

  Investigation of a Mechanism for Accelerated Breakdown of Immune Tolerance to the Primary Biliary Cirrhosis–Associated Autoantigen, Pyruvate Dehydrogenase Complex

  摘要：

  Primary biliary cirrhosis (PBC) is an autoimmune liver disease characterized by autoreactive T- and B-cell responses to the highly conserved enzyme pyruvate dehydrogenase complex (PDC). In this study we have examined the breakdown of T-cell tolerance to self-PDC using a mouse model. Female SJL/J mice were sensitized intraperitoneally with foreign-PDC (bovine) and/or self-PDC (murine) in complete Freund's adjuvant, and serum, spleen, and liver tissue was taken 8 weeks later. Animals sensitized with foreign-PDC produced IgG antibodies that were reactive with both foreign and self-PDC, but splenic T cells from these animals only responded to stimulation with foreign PDC. Sensitization with self-PDC elicited neither antibodies nor reactive T cells. Significantly, cosensitization with mixed self-PDC and foreign-PDC resulted in a full breakdown of self-tolerance, with generation of both antibody and T-cell responses to self-PDC of the type seen exclusively in human PBC patients. Mild bile duct lesions deficient in CD8(+) T cells were seen 8 weeks after sensitization with either foreign or self-PDC. However, after sensitization with mixed self-PDC and foreign-PDC, these lesions were significantly larger and heavily infiltrated by CD8(+) T cells. Liver-infiltrating T cells derived from the self-PDC and foreign-PDC cosensitized but not from control animals showed reactivity with self-PDC, suggesting a possible role for autoreactive PDC-specific T-cell responses in the pathogenesis of the observed histologic changes. It is likely that B-cell cross-reactivity between foreign and self-PDC enhances the potential for breakdown of T-cell self-tolerance by allowing efficient presentation of self-antigens in the inoculum. This model may provide a useful system for investigating the etiology and treatment of PBC.

  DOI：

  10.1038/labinvest.3780413
• 作为产物：
  描述：

  (E,E)-2,4-己二烯醛 在 四丁基氟化铵 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.0h， 生成 octa-4t,6t-dien-1-yn-3-ol
  参考文献：
  名称：

  脱水亚乙基–Co2（CO）6离子：生成，反应性和阳离子稳定性评估

  摘要：

  所述dehydrotropylium钴2（CO）6，通过HBF的作用产生的离子4或BF 3 ⋅ OET 2上的相应cycloheptadienynol复杂，这反过来又在四个步骤制备从一个已知diacetoxycycloheptenyne复杂。环庚二烯炔诺醇络合物通过脱氢tropylium-Co 2（CO）6离子与几个亲核试剂的反应导致与反应性亲核试剂的取代反应（N> 1），并在反应性较低的亲核试剂存在下进行自由基二聚化反应。环庚二烯醇复合物与无环三烯醇复合物的竞争性反应显示，与无环阳离子相比，偏氢萘乙酰-Co 2（CO）6离子的生成没有偏爱。DFT研究了脱氢吡啶鎓-Co 2（CO）6离子，特别是对其芳香族（HOMA）值（+0.95）的谐波振荡器模型，基于同链反应的稳定能（≈2.8kcal mol -1）及其NICS（1）值（-2.9），连同实验研究一起表明，脱氢吡啶鎓-Co 2（CO）6离子是弱芳香族的。

  DOI：

  10.1002/chem.201002685

文献信息

• Gold-Catalyzed Oxidative Cyclization Involving Nucleophilic Attack to the Keto Group of α,α′-Dioxo Gold Carbene and 1,2-Alkynyl Migration: Synthesis of Furan-3-carboxylates
  作者：Ali Wang、Mingduo Lu、Yuanhong Liu

  DOI：10.1021/acs.orglett.1c02389

  日期：2021.9.3

  for the synthesis of functionalized furan-3-carboxylates based on gold-catalyzed oxidative cyclization of diynones with alcohols or water has been developed. Mechanistic studies revealed that a rare nucleophilic attack to the carbonyl group of the α,α′-dioxo gold carbene instead of the carbene center and 1,2-alkynyl group migration were involved in this transformation. This method offers several advantages

  基于金催化二炔酮与醇或水的氧化环化，开发了一种用于合成功能化呋喃-3-羧酸酯的多组分策略。机理研究表明，对 α,α'-二氧代金卡宾的羰基的罕见亲核攻击而不是卡宾中心和 1,2-炔基迁移参与了这种转变。该方法具有多种优势，例如条件温和、区域选择性和化学选择性高以及官能团兼容性广。