2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine | 345217-87-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 金鸡纳生物碱
• 英文名称: 2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine
• 英文别名: O-benzylquinine；quinine benzyl ether；(2S,4S,5R)-2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine；(1S,2S,4S,5R)-2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine；(8I+/-,9R)-6a(2)-Methoxy-9-(phenylmethoxy)cinchonan；4-[(R)-[(2S,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-phenylmethoxymethyl]-6-methoxyquinoline
• CAS: 345217-87-0
• 化学式: C₂₇H₃₀N₂O₂
• 分子量: 414.547
• InChiKey: DVNBDXQSZYGJPC-LKSLQULUSA-N

物化性质

• 沸点：
  549.8±50.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  34.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine 在 sodium hydride 、 N,N'-二环己基碳二亚胺 、 乙硫醇 、 柠檬酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 N-((2S)-1-(3-(4-((1R)-benzyloxy((2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)quinolin-6-yl)thioureido)-3,3-dimethylbutan-2-yl)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Asymmetric Multicomponent Sulfa-Michael/Mannich Cascade Reaction: Synthetic Access to 1,2-Diamino-3-Organosulfur Compounds and 2-Nitro Allylic Amines

  摘要：

  A novel catalytic asymmetric three-component intermolecular sulfa-Michael/Mannich cascade reaction has been developed using a chiral multifunctional catalyst. This reaction provides facile access to 1-amino-2-nitro-3-organosulfur compounds bearing three consecutive stereocenters in high yields (up to 96%) with good diastereo- (up to 91:4:4:1 dr) and excellent enantioselectivities (93-99% ee). Furthermore, the products of this reaction could be facilely transformed into potentially bioactive 1, 2-diamino-3-organosulfur compounds and 2-nitro allylic amines.

  DOI：

  10.1021/acs.orglett.5b02423
• 作为产物：
  描述：

  氯化苄 、 奎宁 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 以100%的产率得到2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine
  参考文献：
  名称：

  包含金鸡纳生物碱铵盐的双功能6'-（硫代）-脲合成的灵活策略

  摘要：

  已经开发了一种灵活且具有官能团耐受性的合成路线，以访问结构上不同的双功能6'-（硫代）-尿素混合物，其中所述双官能6'-（硫）-尿素包含基于金鸡纳生物碱的手性季铵盐。通过这种途径，可以访问超过25种不同的新型含脲和硫脲的铵盐衍生物，这些衍生物到目前为止尚无法获得。

  DOI：

  10.1016/j.tet.2019.130816
• 作为试剂：
  描述：

  苯甲酸 、 环己烯 在 N-溴代丁二酰亚胺(NBS) 、 2-((R)-(benzyloxy)(6-methoxyquinolin-4-yl)methyl)-5-vinylquinuclidine 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以80%的产率得到2-bromocyclohexyl benzoate
  参考文献：
  名称：

  First asymmetric intermolecular bromoesterification catalyzed by chiral Brønsted acid

  摘要：

  The first successful enantioselective intermolecular bromoesterification was realized by using a chiral phosphoric acid as a catalyst. The reaction was optimized after screening 2-aminopyridine based basic catalysts. cinchona alkaloid based basic catalysts, and binol backbone based Bronsted acid catalysts. Up to 70% ee and a moderate yield were achieved under the optimized condition. An ion-pair mechanism has been suggested in order to explain the reaction results. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.02.016

文献信息

• Metal-Free, Phosphonium Salt-Mediated Sulfoximination of Azine <i>N</i>-Oxides: Approach for the Synthesis of <i>N</i>-Azine Sulfoximines
  作者：Sravan Kumar Aithagani、Mukesh Kumar、Mahipal Yadav、Ram A. Vishwakarma、Parvinder Pal Singh

  DOI：10.1021/acs.joc.6b00593

  日期：2016.7.15

  method for the synthesis of N-azine sulfoximines by the nucleophilic substitution of azine N-oxides with NH-sulfoximines. The present method works at room temperature with wide functional group compatibility and gives several unprecedented N-azine sulfoximines. The reaction conditions were also found suitable with enantiopure substrates and furnished products without any racemization. It also finds

  在本文中，我们报道了一种简单且无金属的方法，该方法通过用NH-亚砜肟酮亲核取代N-嗪氮氧化物来合成N-嗪亚砜肟。本方法在室温下具有宽泛的官能团相容性，并提供了几种前所未有的N-嗪亚磺酰亚胺。还发现反应条件适用于对映纯底物和提供的产物，没有任何消旋作用。还发现了其在基于嗪的功能分子如2,2'-联吡啶，1,10-菲咯啉和奎宁的磺化中的应用。
• Trifluoromethylation of Unactivated Alkenes with Me₃SiCF₃ and <i>N</i>-Iodosuccinimide
  作者：Xinkan Yang、Gavin Chit Tsui

  DOI：10.1021/acs.orglett.9b00332

  日期：2019.3.1

  A novel approach to the trifluoromethylation of unactivated alkenes is presented. This reaction is promoted by N-iodosuccinimide (NIS) under visible light irradiation without the need for photocatalysts. The mild conditions allow the direct synthesis of useful trifluoromethylated (E)-alkenes from readily available alkene feedstocks with excellent functional group tolerability. In addition, using easy-to-handle

  提出了一种对未活化烯烃进行三氟甲基化的新方法。N-碘代琥珀酰亚胺（NIS）在可见光照射下可促进该反应，而无需光催化剂。温和的条件允许从容易获得的具有优异的官能团耐受性的烯烃原料直接合成有用的三氟甲基化的（E）-烯烃。此外，对于工业规模的应用，使用易于操作的商业化Me 3 SiCF 3代替气态CF 3 I作为CF 3源是非常有吸引力的。
• Radical C−H Acylation of Nitrogen Heterocycles Induced by an Aerobic Oxidation of Aldehydes
  作者：Subhasis Paul、Manotosh Bhakat、Joyram Guin

  DOI：10.1002/asia.201900857

  日期：2019.9.16

  ketones is described herein. The reaction involves cross-dehydrogenative coupling between aldehydes and heteroaromatic bases with molecular oxygen (O2 ). The key aspect of the method is the generation of reactive acyl radical via homolytic activation of aldehyde C-H bond using O2 as the sole oxidant. The reaction has a good substrate scope with respect to aldehydes and functionalized nitrogen heterocycles

  本文描述了用于合成不对称杂芳基酮的需氧自由基方法。该反应涉及醛和杂芳族碱与分子氧（O2）之间的交叉脱氢偶联。该方法的关键方面是使用O2作为唯一氧化剂，通过醛CH键的均质活化来生成反应性酰基基团。关于醛和官能化的氮杂环，该反应具有良好的底物范围。根据我们的机理研究，建议该反应采用自由基链途径。该方法的合成应用在天然生物碱（±）安格西汀的形式合成中得到了证明。
• Enantioselective α-Hydroxylation of β-Keto Esters Catalyzed by Cinchona Alkaloid Derivatives
  作者：Qingwei Meng、Yakun Wang、Zhi Li、Ting Xiong、Jingnan Zhao

  DOI：10.1055/s-0034-1378548

  日期：——

  A highly efficient α-hydroxylation of β-keto esters catalyzed by cupreidine in the presence of cumyl hydroperoxide (CHP) was achieved. The reaction was applied to a wide variety of β-keto esters to give products in high yields (up to 95%) with excellent enantioselectivities (up to 97% ee). The reaction had been successfully scaled up to a gram quantity and (S)-5-chloro-2-hydroxy-1-oxo-2,3-dihydro-

  在枯基氢过氧化物（CHP）存在下，实现了由铜吡啶催化的β-酮酯的高效α-羟基化。该反应适用于多种 β-酮酯，以高产率（高达 95%）得到具有优异对映选择性（高达 97% ee）的产物。该反应已成功放大到克级，并且 (S)-5-chloro-2-hydroxy-1-oxo-2,3-dihydro-1H-indene-2-carboxylate – 茚虫威的重要中间体在96% 收率和 86% ee。通过结晶可将对映体过量提高到99%，该方法具有对映选择性高、催化剂易于制备和催化剂回收等优点，具有工业应用前景。
• One-Pot Anti-Markovnikov Hydroamination of Unactivated Alkenes by Hydrozirconation and Amination
  作者：Alexandra E. Strom、John F. Hartwig

  DOI：10.1021/jo401498w

  日期：2013.9.6

  A one-pot anti-Markovnikov hydroamination of alkenes is reported. The synthesis of primary and secondary amines from unactivated olefins was accomplished in the presence of a variety of functional groups. Hydrozirconation, followed by amination with nitrogen electrophiles, provides exclusive anti-Markovnikov selectivity. Most products are isolated in high yields without the use of column chromatography

  报道了烯烃的一锅抗马尔科夫尼科夫加氢胺化反应。由未活化烯烃合成伯胺和仲胺是在各种官能团的存在下完成的。氢化锆，然后用氮亲电试剂胺化，提供独特的抗马尔科夫尼科夫选择性。大多数产品以高产率分离，无需使用柱层析。