1-cyclohexyl-3,4-dihydro-6,7-dimethoxyisoquinoline | 69743-45-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢异喹啉
• 英文名称: 1-cyclohexyl-3,4-dihydro-6,7-dimethoxyisoquinoline
• 英文别名: 6,7-dimethoxy-1-cyclohexyl-3,4-dihydroisoquinoline；1-cyclohexyl-6,7-dimethoxy-3,4-dihydro-isoquinoline；1-Cyclohexyl-6,7-dimethoxy-3,4-dihydro-isochinolin；1-Cyclohexyl-6,7-dimethoxy-3,4-dihydroisoquinoline；1-cyclohexyl-6,7-dimethoxy-3,4-dihydroisoquinoline
• CAS: 69743-45-9
• 化学式: C₁₇H₂₃NO₂
• 分子量: 273.375
• InChiKey: CRJZSPPHKHBVTK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-cyclohexyl-3,4-dihydro-6,7-dimethoxyisoquinoline 在 lead(IV) acetate 、 三乙胺 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 19.0h， 生成 1',5',6',10b'-tetrahydro-8',9'-dimethoxy-10b-(trichloromethyl)spiro-1,1'-[3H-oxazolo][4,3-a]isoquinolin-3'-one
  参考文献：
  名称：

  1-亚烷基-1,2,3,4-四氢-2-（三氯乙酰基）异喹啉氧化重排为1,5,6,10b-四氢-10b-（三氯甲基）-3 H-恶唑[4,3- a ] isoquinolin-3-ones

  摘要：

  用四乙酸铅（Pb（OAc）4）处理后，1-（亚烷基）-1,2,3,4-四氢-N-（三氯乙酰基）异喹啉2a - 2c以及三溴乙酰基衍生物4经历氧化环化伴随三卤代甲基的迁移，得到1,5,6,10b-四氢-10b-（三氯甲基）-3 H-恶唑并[4,3- a ]异喹啉-3-酮3a – 3c或三溴甲基衍生物6， 分别。这些三环化合物也可以通过3,4-二氢-1-（1-羟基-1-甲基乙基）异喹啉8的酯化反应获得分别使用三氯乙酰氯或三溴乙酰溴。对这些反应的合理的机理描述涉及到前所未有的“分子内亚氨基卤形”重排。

  DOI：

  10.1002/hlca.200490065
• 作为产物：
  描述：

  1-cyclohexyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 在 1,10-邻二氮杂菲-5,6-二酮 、 氧气 、 4-甲基苯磺酸吡啶 、 zinc(II) iodide 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以90%的产率得到1-cyclohexyl-3,4-dihydro-6,7-dimethoxyisoquinoline
  参考文献：
  名称：

  Bioinspired Aerobic Oxidation of Secondary Amines and Nitrogen Heterocycles with a Bifunctional Quinone Catalyst

  摘要：

  Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  DOI：

  10.1021/ja411692v

文献信息

• Robust cyclometallated Ir(iii) catalysts for the homogeneous hydrogenation of N-heterocycles under mild conditions
  作者：Jianjun Wu、Jonathan H. Barnard、Yi Zhang、Dinesh Talwar、Craig M. Robertson、Jianliang Xiao

  DOI：10.1039/c3cc44567d

  日期：——

  Cyclometallated Cp*Ir(N∧C)Cl complexes derived from N-aryl ketimines are highly active catalysts for the reduction of N-heterocycles under ambient conditions and 1 atm H2 pressure. The reaction tolerates a broad range of other potentially reducible functionalities and does not require the use of specialised equipment, additives or purified solvent.

  由N-芳基亚胺衍生的环金属化Cp*Ir(N∧C)Cl配合物是在常温常压下对N-杂环进行还原的高度活性催化剂。该反应能容忍多种潜在可还原官能团，无需使用特殊设备、添加剂或纯净溶剂。
• Acceptorless Dehydrogenation of Nitrogen Heterocycles with a Versatile Iridium Catalyst
  作者：Jianjun Wu、Dinesh Talwar、Steven Johnston、Ming Yan、Jianliang Xiao

  DOI：10.1002/anie.201300292

  日期：2013.7.1

  Gas up: A cyclometalated iridium complex is found to catalyze the dehydrogenation of various benzofused N‐heterocycles, thus releasing H2. Driven by as low as 0.1 mol % catalyst, the reaction affords quinolines, indoles, quinoxalines, isoquinolines, and β‐carbolines in high yields.

  放气：发现一种环金属化的铱络合物可催化各种苯并稠合的N-杂环的脱氢反应，从而释放出H 2。在低至0.1 mol％的催化剂的驱动下，该反应可高产率提供喹啉，吲哚，喹喔啉，异喹啉和β-咔啉。
• Driving Recursive Dehydration by P^III/P^V Catalysis: Annulation of Amines and Carboxylic Acids by Sequential C–N and C–C Bond Formation
  作者：Morgan Lecomte、Jeffrey M. Lipshultz、Shin-Ho Kim-Lee、Gen Li、Alexander T. Radosevich

  DOI：10.1021/jacs.9b06277

  日期：2019.8.14

  A method for the annulation of amines and carboxylic acids to form pharmaceutically relevant azaheterocycles via organophosphorus PIII/PV redox catalysis is reported. The method employs a phosphetane catalyst together with a mild bromenium oxidant and terminal hydrosilane reductant to drive successive C–N and C–C bond-forming dehydration events via the serial action of a catalytic bromophosphonium

  报道了一种通过有机磷 PIII/PV 氧化还原催化将胺和羧酸环化形成药学相关氮杂杂环的方法。该方法使用磷烷催化剂以及温和的溴鎓氧化剂和末端氢硅烷还原剂，通过催化溴鏻中间体的串联作用来驱动连续的 C-N 和 C-C 键形成脱水事件。这些结果证明了 PIII/PV 氧化还原催化的能力，能够实现重复的氧化还原中性转化，以补充 PIII/PV 对的共同还原驱动力。
• Asymmetric Transfer Hydrogenation of Imines in Water by Varying the Ratio of Formic Acid to Triethylamine
  作者：Vaishali S. Shende、Sudhindra H. Deshpande、Savita K. Shingote、Anu Joseph、Ashutosh A. Kelkar

  DOI：10.1021/acs.orglett.5b00889

  日期：2015.6.19

  Asymmetric transfer hydrogenation (ATH) of imines has been performed with variation in formic acid (F) and triethylamine (T) molar ratios in water. The F/T ratio is shown to affect both the reduction rate and enantioselectivity, with the optimum ratio being 1.1 in the ATH of imines with the Rh-(1S,2S)-TsDPEN catalyst. Use of methanol as a cosolvent enhanced reduction activity. A variety of imine substrates

  亚胺的不对称转移氢化（ATH）随水中甲酸（F）和三乙胺（T）摩尔比的变化而变化。已显示出F / T比影响还原速率和对映选择性，在具有Rh-（1 S，2 S）-TsDPEN催化剂的亚胺的ATH中，最佳比为1.1 。使用甲醇作为助溶剂可增强还原活性。减少了各种亚胺底物，提供了高收率（94–98％）和良好至优异的对映选择性（89–98％）。与普通的共沸FT系统相比，以1.1 / 1 F / T降低速度更快。
• An Enantioselective Inverse‐Electron‐Demand Imino Diels–Alder Reaction
  作者：Vincent Eschenbrenner‐Lux、Philipp Küchler、Slava Ziegler、Kamal Kumar、Herbert Waldmann

  DOI：10.1002/anie.201309022

  日期：2014.2.17

  The imino Diels–Alder reaction is an efficient method for the synthesis of aza‐heterocycles. While different stereo‐ and enantioselective inverse‐electron‐demand imino Diels–Alder (IEDIDA) reactions have been reported before, IEDIDA reactions including electron‐deficient dienes are unprecedented. The first enantioselective IEDIDA reaction between electron‐poor chromone dienes and cyclic imines, catalyzed

  亚氨基Diels–Alder反应是合成氮杂杂环的有效方法。虽然以前已经报道了不同的​​立体和对映选择性反电子需求的亚氨基狄尔斯-阿尔德（IEDIDA）反应，但包括电子缺陷二烯在内的IEDIDA反应是前所未有的。描述了锌/比诺醇配合物催化的贫电子色酮二烯与环状亚胺之间的第一个对映选择性IEDIDA反应。新颖的反应为加入天然产物的环状融合喹啉衍生物（包括有效的有丝分裂调节剂）提供了便捷的入口。