(1S,4R)-1,4-dimethyl-1,2,3,4-tetrahydroisoquinoline | 503822-60-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (1S,4R)-1,4-dimethyl-1,2,3,4-tetrahydroisoquinoline
• CAS: 503822-60-4
• 化学式: C₁₁H₁₅N
• 分子量: 161.247
• InChiKey: ICXDKWHGNNFJOU-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  对甲苯磺酰氯 、 (1S,4R)-1,4-dimethyl-1,2,3,4-tetrahydroisoquinoline 在 N,N-二异丙基乙胺 作用下， 生成 (1S,4R)-N-tosyl-1,4-dimethyl-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  通过6- exo自由基环化反应合成对映体纯的单取代和双取代的四氢异喹啉

  摘要：

  由（-）-8-氨基薄荷醇衍生的2-（邻溴苯基）-3-烯丙基和2-烯丙基-3-（邻溴苄基）取代的全氢苯并恶嗪易于在存在下与氢化三丁基锡反应而立体选择性地环化AIBN。通过用氢化铝锂还原N，O-乙缩醛部分的开环，将环化化合物转化为对映体纯的4-烷基四氢异喹啉。对映体纯的1,4-和3,4-二烷基取代的四氢异喹啉还可以通过环化的化合物与甲基碘化镁反应，然后消除薄荷醇附肢而制备。

  DOI：

  10.1016/s0040-4020(01)00274-5
• 作为产物：
  描述：

  (1R,2S,5R)-2-[1-((1S,4R)-1,4-Dimethyl-3,4-dihydro-1H-isoquinolin-2-yl)-1-methyl-ethyl]-5-methyl-cyclohexanol 在 氢氧化钾 、 3 A molecular sieve 、 sodium acetate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 (1S,4R)-1,4-dimethyl-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  通过6- exo自由基环化反应合成对映体纯的单取代和双取代的四氢异喹啉

  摘要：

  由（-）-8-氨基薄荷醇衍生的2-（邻溴苯基）-3-烯丙基和2-烯丙基-3-（邻溴苄基）取代的全氢苯并恶嗪易于在存在下与氢化三丁基锡反应而立体选择性地环化AIBN。通过用氢化铝锂还原N，O-乙缩醛部分的开环，将环化化合物转化为对映体纯的4-烷基四氢异喹啉。对映体纯的1,4-和3,4-二烷基取代的四氢异喹啉还可以通过环化的化合物与甲基碘化镁反应，然后消除薄荷醇附肢而制备。

  DOI：

  10.1016/s0040-4020(01)00274-5

文献信息

• New insight into the role of a base in the mechanism of imine transfer hydrogenation on a Ru(ii) half-sandwich complex
  作者：Marek Kuzma、Jiří Václavík、Petr Novák、Jan Přech、Jakub Januščák、Jaroslav Červený、Jan Pecháček、Petr Šot、Beáta Vilhanová、Václav Matoušek、Iryna I. Goncharova、Marie Urbanová、Petr Kačer

  DOI：10.1039/c3dt32733g

  日期：——

  overall mechanism could be more significant than generally accepted. The hydrogenation mixture was studied by nuclear magnetic resonance (NMR), Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and vibrational circular dichroism (VCD) with infrared spectroscopy. The results suggested that the protonated base formed an associate with the active ruthenium-hydride species, most probably

  将[RuCl（η使用环状亚胺的不对称转移氢化（ATH）6 - p TsDPEN -cymene）]（TsDPEN = Ñ-tosyl-1,2-diphenylethylenediamine）已与HCOOH-基础氢供体混合物中使用的各种脂族（仲，叔）和芳族胺进行了测试。观察到反应速率和立体选择性方面的显着差异，这表明一个事实，即碱在整个机理中的作用可能比通常所接受的更为重要。通过核磁共振（NMR），傅立叶变换离子回旋共振质谱（FT-ICR MS）和振动圆二色性（VCD）和红外光谱研究了氢化混合物。结果表明，质子化碱与活性氢化钌物质缔合，最有可能通过与配合物的磺酰基形成氢键。假定碱基之间的空间和电子差异是造成最初ATH实验结果的原因。
• Aryl Radical Cyclization of Chiral 3-Allyl-2-(2-bromophenyl)-1,3-oxazolidines with Tributyltin Hydride
  作者：Kimio Higashiyama、Takayasu Yamauchi、Jumpei Sugiyama

  DOI：10.3987/com-02-s(m)42

  日期：——
• Conformational Analysis. 50. <i>C</i>-Methyl-1,2,3,4-tetrahydroisoquinolines
  作者：Edward M. Olefirowicz、Ernest L. Eliel

  DOI：10.1021/jo971257r

  日期：1997.12.1

  Conformational equilibria in 1-, 3-, and 4-methyl-1,2,3,4-tetrahydroisoquinolines (THIQs) and the diastereomeric pairs of their 1,3- and 1,4-dimethyl homologs have been determined by measurement of H-3/H-4(trans) coupling constants and have been confirmed by molecular mechanics [MMP2(85]) calculations. The experimental -Delta G degrees values (a --> e) for the monomethyl compounds (computed values in parentheses) in kcal mol(-1) are Me-1, 0.56 (0.46); Me-3, 1.63 (1.53); and Me-4, -0.32 (-0.22). Agreement of experimental and calculated values is very goad as is the additivity of values for the dimethyl compounds (Table 1). Values for the corresponding hydrochlorides are Me-1, 0.19 (-0.34); Me-3, 1.15 (1.46); and Me-4, 0.35 (0.10) kcal mol(-1). The less than satisfactory agreement of experimental with computed data here is probably due to neglect of solvation. The very small or negative Delta G degrees values for Me-1 and Me-4 were ascribed not only to the pseudoaxial (rather than axial) nature of Me(ax) and the absence of a syn-axial hydrogen on the side of the benzene ring but also to a peri interaction with H(8) and H(5), respectively, destabilizing equatorial methyl at positions 1 and 4. This was confirmed by comparing computed conformational energy values with values at corresponding positions in Delta(3,4)-tetrahydropyridines (THPs). While Delta G degrees in the two series is the same for Me-3 (THIQ numbering), that for Me-1 and Me-4 is considerably smaller in the THIQ than in the THP series which latter is devoid of peri hydrogens.
• Synthesis of enantiopure mono- and disubstituted tetrahydroisoquinolines by 6-exo radical cyclizations
  作者：Rafael Pedrosa、Celia Andrés、Jesús M Iglesias、Manuel A Obeso

  DOI：10.1016/s0040-4020(01)00274-5

  日期：2001.4

  menthol, readily cyclized stereoselectively by reaction with tributyltin hydride in the presence of AIBN. The cyclization compounds were transformed into enantiopure 4-alkyl tetrahydroisoquinolines by reductive ring opening of the N,O-acetal moiety with lithium aluminum hydride. Enantiopure 1,4- and 3,4-dialkyl-substituted tetrahydroisoquinolines were also prepared by reaction of the cyclized compounds

  由（-）-8-氨基薄荷醇衍生的2-（邻溴苯基）-3-烯丙基和2-烯丙基-3-（邻溴苄基）取代的全氢苯并恶嗪易于在存在下与氢化三丁基锡反应而立体选择性地环化AIBN。通过用氢化铝锂还原N，O-乙缩醛部分的开环，将环化化合物转化为对映体纯的4-烷基四氢异喹啉。对映体纯的1,4-和3,4-二烷基取代的四氢异喹啉还可以通过环化的化合物与甲基碘化镁反应，然后消除薄荷醇附肢而制备。