10,11-didehydroquincoridine | 219794-74-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 奎宁环
• 英文名称: 10,11-didehydroquincoridine
• 英文别名: didehydroquincoridine；10,11-Didehydro-quincoridine；[(2R,4S,5S)-5-ethynyl-1-azabicyclo[2.2.2]octan-2-yl]methanol
• CAS: 219794-74-8
• 化学式: C₁₀H₁₅NO
• 分子量: 165.235
• InChiKey: BAROCKUOBIXNNQ-LPEHRKFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  10,11-didehydroquincoridine 在 三乙胺 、 lithium iodide 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 生成 (1S,2R,4S,5S)-2-iodomethyl-5-ethynyl-1-azabicyclo[2.2.2]octane
  参考文献：
  名称：

  Synthesis of Enantiopure 1-Azabicyclo[3.2.2]nonanes via Stereoselective Capture of Chiral Carbocations

  摘要：

  [GRAPHICS]A new class of doubly functionalized and enantiomerically pure 1-azabicyclo[3.2.2]nonanes derived from quincorine and quincoridine is described. 2,5-Disubstituted quinuclidines with a C9-mesyloxy group were easily transformed into the corresponding halides upon treatment with lithium salts. Subsequent silver salt-mediated ring expansion stereoselectively furnished the title azabicyclics. Chiral carbocations which are configurationally stable and nonplanar are postulated to account for the striking stereoselectivity of the capture of external nucleophile. 5-Ethynyl-2-iodomethylquinuclidines afford the alpha-benzoyloxy amines rather than alpha-methoxy amines, even in MeOH.

  DOI：

  10.1021/ol0057378
• 作为产物：
  描述：

  quincoridine 在 溴 、 sodium hydroxide 、 甲基三辛基氯化铵 作用下， 以 氯仿 、 叔丁醇 为溶剂， 反应 6.0h， 生成 10,11-didehydroquincoridine
  参考文献：
  名称：

  PdII 和 PtII 配合物与 Quincorine 和 Quincoridine 衍生物的合成和结构研究

  摘要：

  已经合成了一系列 PdII-quincorine 和 -quincoridine 配合物，其中配体通过 N,O-供体原子配位，并通过 X 射线晶体学确定了它们的结构特征。此外，还获得了新的手性四齿 N,P-配体，其中包含通过顺式-烯二炔片段桥接的两个奎宁环核心。强调了含有两个软磷和两个硬氮供体的新配体对 PdII 和 PtII 的不同配位特性。几种典型的配合物通过 X 射线晶体学在结构上进行了表征。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300557

文献信息

• Cross-coupling reactions in Cinchona alkaloid chemistry: aryl-substituted and dimeric quinine, quinidine, as well as quincorine and quincoridine derivatives
  作者：Jens Frackenpohl、Wilfried M. Braje、H. Martin R. Hoffmann

  DOI：10.1039/b004693k

  日期：——

  Cross-coupling reactions of modified Cinchona alkaloids provide access to a wide variety of novel arylated and dimeric derivatives of quinine and quinidine containing a single and double 1,2-amino alcohol functionality. Sonogashira and Heck reactions allow functionalization of ethynyl and 11-iodovinyl precursors. The role of bystander functionality is investigated.

  改良Cincona生物碱的交叉耦合反应可以合成多种新型的芳基化和二聚体奎宁及奎尼丁衍生物，包含单一和双重的1,2-氨醇功能团。Sonogashira和Heck反应允许对乙炔和11-碘乙烯前体进行功能化。研究了旁观者功能团的作用。
• Synthesis of new quinuclidine derivatives via Pd-mediated cross-coupling and cross-benzannulation reactions
  作者：Stefania Tötös、Manfred Fild、Carsten Thöne、Ion Grosu

  DOI：10.1016/j.tet.2009.05.030

  日期：2009.8

  palladium-catalyzed addition reactions of terminal alkynes (donors) to internal alkynes (acceptors). The enantiopure terminal alkynes were derivatives of quincoridine and quincorine, two semi-natural Cinchona alkaloids. The processes exhibited high chemoselectivity and excellent diastereoselectivity, the E-enynes being obtained as single products in almost all cases. The synthesis of new tetra and pentasubstituted

  通过钯催化的末端炔烃（供体）与内部炔烃（受体）的加成反应制备了新的官能化奎核苷。对映体纯的末端炔烃是两种半天然金鸡纳生物碱喹可啶和喹可林的衍生物。该方法显示出高的化学选择性和出色的非对映选择性，E-烯炔几乎在所有情况下均作为单一产品获得。通过二炔的[2 + 2 + 2]苯并环合成高收率的新的四和五取代的苯衍生物，这是通过钯催化的10,11-二氢喹可啶和10,11-二氢喹可啶的钯二聚化，并带有末端炔烃报道了通过[4 + 2]使10，11-二氢喹可啶的烯炔衍生物与2，4-己烷-二炔的苯并环形成有可观的收率。
• New Members of the Cinchona Alkaloids Family: Assembly of the Triazole Heterocycle at the 6′ Position
  作者：Catalin Vasile Maftei、Martin Heiko Franz、Christian Kleeberg、Ion Neda

  DOI：10.3390/molecules26113357

  日期：——

  The substance class of the well-known Cinchona alkaloids is widened by 6′-Amino-cinchonine and 6′-Amino-cinchonidine, novel compounds which incorporate a primary amino function in the quinolinic ring system. These key intermediates open the field for a range of fruitful chemistry. Here is described a short and direct pathway for the synthesis of triazole containing derivatives of the above-mentioned

  著名的金鸡纳的物质类别生物碱被 6'-氨基-辛可宁和 6'-氨基-辛可尼丁扩展，这是在喹啉环系统中加入伯氨基官能团的新型化合物。这些关键中间体为一系列富有成效的化学开辟了领域。这里描述了使用 [3 + 2] Huisgen 环加成反应合成上述物质的含三唑衍生物的短而直接的途径。为此，首先将胺转化为相应的叠氮化物。在此基础上，合成了未取代和甲硅烷基保护的三唑作为实例。此外，喹可啉和喹可啶的二脱水衍生物被用作加成伙伴，导致在两端带有金鸡纳生物碱奎宁环的化合物。对这些化合物中的一些进行放射照相检查以研究奎宁环与三唑的位置。化合物的固态结构10，11和28是由X射线衍射分析来确定。
• Synthesis of 10,11-didehydro- and 10,11-dihydro-Quincorine and of the Quincoridine analogs: functionalized and enantiopure 1-azabicyclo[2.2.2]-octanes with four stereogenic centers
  作者：Olaf Schrake、Wilfried Braje、H.M.R. Hoffmann、R. Wartchow

  DOI：10.1016/s0957-4166(98)00364-4

  日期：1998.10

  The convenient synthesis of 10,11-didehydro-QCI (2) and of 10,11-didehydro-QCD (4) as well as 10,11-dihydro-QCI (5) and 10,11-dihydro-QCD (6) is described. Conversion of the olefinic double bond of Quincorine®1 and Quincoridine®3 into the corresponding alkynes 2 and 4 involves twofold dehydrobromination, and an important application of the solid KOH/aliquat 336 system in the key step. The structure

  方便合成10,11-二氢-QCI（2）和10,11-二氢-QCD（4）以及10,11-二氢-QCI（5）和10,11-二氢-QCD（6）描述。Quincorine的烯属双键的转化率® 1和Quincoridine ® 3为相应的炔烃2和4涉及双重脱溴化氢，并将固体KOH的一个重要应用/ ALIQUAT在关键步骤336系统。X射线晶体衍射已阐明了二氢-QCI（2）的结构。新炔烃2和4 分别比QCI和QCD更具极性和更基础。
• New hydrogenated and didehydrogenated 1,2-diamines of quincorine and quincoridine
  作者：Ion Neda、Thomas Kaukorat、Christian Hrib

  DOI：10.1016/s0957-4166(02)00320-8

  日期：2002.7

  Four new members of the family of 1,2-diamines of quincorine and quincoridine have been synthesized, being hydrogenated and didehydrogenated at the C10-C11 fragment. The alkynes, containing an additional amino group at C9, are potentially useful building blocks for cross-coupling reactions. Additional investigations concerning the chemical properties of the molecules point to a significant impact of the remote C5 substituent on the basicity of the bridgehead nitrogen. (C) 2002 Elsevier Science Ltd. All rights reserved.