(1S,5S,6S,7S)-10,10-dimethyl-3,3-dioxo-5,6-bis(2-phenylethynyl)-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-6-ol | 185134-85-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,5S,6S,7S)-10,10-dimethyl-3,3-dioxo-5,6-bis(2-phenylethynyl)-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-6-ol
• CAS: 185134-85-4
• 化学式: C₂₆H₂₅NO₃S
• 分子量: 431.555
• InChiKey: UCXDGFDCJQSIKK-MNPUUQGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  74.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,5S,6S,7S)-10,10-dimethyl-3,3-dioxo-5,6-bis(2-phenylethynyl)-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-6-ol 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以60%的产率得到(3aS,6aS,9aS)-7-(Z-2-chloro-2-phenylmethylene)-6a-hydroxy-10,10-dimethyl-8-phenyl-3a,4,5,6,6a,7-hexahydro-1H,3H-3a,6-methano-indeno[3a,4-c]isothiazole 2,2-dioxide
  参考文献：
  名称：

  Diyne Cyclization in Camphor Derivatives - Experimental and Theoretical Investigation

  摘要：

  3-氧代樟脑磺酰亚胺（1）的衍生物，其内部位置的碳原子C-2和C-3上带有两个苯乙炔基团，已制备，并研究了它们对卤素和氯化钛的反应性。在每种情况下，两个乙炔基团导致了一个五元环的融合，形成了取决于位于位置3的附加取代基的体积的方向的双环[2.2.1]系统。NMR研究表明，类似6和8的阳离子物种是第一个可检测到的中间体。它们不仅包含融合的五元环，还包括外环亚甲基碳和磺酰基氧原子之间的键，从而将正电荷主要转移到硫上。半经验计算（PM3）建议在形成这种阳离子过程中存在两个中间体。

  DOI：

  10.1515/znb-1996-1121
• 作为产物：
  描述：

  (-)-3-oxocamphorsulfonyl imine 、 苯乙炔 在 正丁基锂 作用下， 生成 (1S,5S,6S,7S)-10,10-dimethyl-3,3-dioxo-5,6-bis(2-phenylethynyl)-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-6-ol
  参考文献：
  名称：

  Diyne Cyclization in Camphor Derivatives - Experimental and Theoretical Investigation

  摘要：

  3-氧代樟脑磺酰亚胺（1）的衍生物，其内部位置的碳原子C-2和C-3上带有两个苯乙炔基团，已制备，并研究了它们对卤素和氯化钛的反应性。在每种情况下，两个乙炔基团导致了一个五元环的融合，形成了取决于位于位置3的附加取代基的体积的方向的双环[2.2.1]系统。NMR研究表明，类似6和8的阳离子物种是第一个可检测到的中间体。它们不仅包含融合的五元环，还包括外环亚甲基碳和磺酰基氧原子之间的键，从而将正电荷主要转移到硫上。半经验计算（PM3）建议在形成这种阳离子过程中存在两个中间体。

  DOI：

  10.1515/znb-1996-1121

文献信息

• Cleavage of acetylenic substituents from camphor-derivatives by copper(I) chloride
  作者：M.F.N.N. Carvalho、T.A. Fernandes、A.S.D. Ferreira、L.G. Alves、R. Herrmann

  DOI：10.1016/j.jorganchem.2008.06.004

  日期：2008.8

  cleavage of acetylenic substituents from the camphor skeleton of compounds 1 containing two C–C triple bonds as well as from the compounds 6 and 7 containing one. This is a formal reversal of the formation of these compounds by the reaction of acetylides with keto and imino groups in compound 18. The substituent R at the triple bond modifies the reactivity and regioselectivity. As intermediates in the process

  氯化铜（I）被发现是一种高效的试剂，可促进乙炔替代物从含有两个C-C三键的化合物1的樟脑骨架以及含有一个CC-C三键的化合物6和7裂解。这是化合物18中乙炔化物与酮基和亚氨基反应形成的这些化合物的形式上的正式逆转。三键上的取代基R改变了反应性和区域选择性。作为过程中的中间体，我们确定了[Cu（L）depr ]类型的配合物（其中（L）depr表示去质子化的樟脑衍生的配体（L））和[CuCl（L）]。量子力学计算支持并合理化实验结果。
• Cascade Reaction of Camphor-Derived Diynes with Transition Metal Compounds
  作者：M. Fernanda N. N. Carvalho、Armando J. L. Pombeiro、Gabriele Wagner、Bjørn Pedersen、Rudolf Herrmann

  DOI：10.1515/znb-1999-0604

  日期：1999.6.1

  Platinum(II) catalyzes the isomerization of camphor sulfonamide diynes in a cascade reaction involving annulation of a five-membered ring to the camphor skeleton, ring-enlargement by C-C bond cleavage, reduction of sulfur(VI) to sulfur(IV), and oxidation of a hydroxy group to a ketone. The reactions of the diynes with other transition metal compounds were also studied. Copper, gold and rhenium give

  铂 (II) 在级联反应中催化樟脑磺酰胺二炔的异构化，包括将五元环环化到樟脑骨架、通过 CC 键裂解扩大环、硫 (VI) 还原为硫 (IV) 和氧化羟基变成酮。还研究了二炔与其他过渡金属化合物的反应。铜、金和铼提供的最终产品类似于使用简单的布朗斯台德酸或卤素获得的最终产品，主要是通过将五元环与樟脑部分成环，同时将磺酰胺还原为亚磺酰胺基团，但缺少扩环步骤. 钯 (II) 占据中间位置，因为获得了两种类型的产品。讨论了反应机理和中间体
• Synthesis and catalytic activity of camphor titanium complexes
  作者：M. Fernanda N.N. Carvalho、Adelino M. Galvão、Jana Kredatusová、Jan Merna、Pedro F. Pinheiro、M. Margarida Salema

  DOI：10.1016/j.ica.2011.11.019

  日期：2012.3

  Three new camphor-titanium complexes [TiClCp2L] (L = L-1, (1); L-2, (2) and (LH)-L-3 (3)) were obtained through replacement of one chloride by a camphor-type ligand ((LH)-L-1, (LH)-L-2, (LH2)-L-3 (3)) at the coordination sphere of [TiCl2Cp2]. Complexes 1 and 2 were structurally characterized by X-ray diffraction analysis showing that coordination occurs through the oxygen atom of the hydroxo group (1) with cooperative coordination of the nitrogen atom of the oxime complex in 2. Upon activation with MAO complexes 1 and 2 promote ethylene polymerization and ethylene/norbornene co-polymerization while compound 3 displays no catalytic activity for either one or the other process. At 50 degrees C the catalytic activity complex of 2 (852 kg(PE) mol (1) h (1)) for ethylene polymerization is higher than that of compound 1 (668 kg(PE) mol (1) h (1)) which is similar to that of [TiCl2Cp2] (670 kg PE mol (1) h (1)). The catalytic activity of complex 1 displays a higher dependence on the temperature than that of compound 2 which is attributed to the strength of the Ti-O bond that renders generation of the active site more difficult in 1. Compounds 1 and 2 are also active catalysts for co-polymerization of ethylene with norbornene affording copolymers with approximately 15 mol% of norbornene content.The microstructures of the polyethylenes and ethylene norbornene co-polymers were checked by NMR and their melting points were measured by DSC. (C) 2011 Elsevier B. V. All rights reserved.
• Wagner, Gabriele; Herrmann, Rudolf; Schier, Annette, Journal of the Chemical Society. Perkin transactions I, 1997, # 5, p. 701 - 707
  作者：Wagner, Gabriele、Herrmann, Rudolf、Schier, Annette

  DOI：——

  日期：——