(6R,8R)-(-)-2-chloro-5,6,7,8,-tetrahydro-7,7-dimethyl-[6,8-methanoquinoline] | 304857-39-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (6R,8R)-(-)-2-chloro-5,6,7,8,-tetrahydro-7,7-dimethyl-[6,8-methanoquinoline]
• 英文别名: 2-chloro-6,8-methano-7,7-dimethyl-5,6,7,8-tetrahydroquinoline；(1R,9R)-4-chloro-10,10-dimethyl-3-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 304857-39-4
• 化学式: C₁₂H₁₄ClN
• 分子量: 207.703
• InChiKey: ADKGYVVPFSQIBR-IUCAKERBSA-N

物化性质

• 沸点：
  290.5±40.0 °C(Predicted)
• 密度：
  1.162±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (6R,8R)-(-)-2-chloro-5,6,7,8,-tetrahydro-7,7-dimethyl-[6,8-methanoquinoline] 在 nickel dichloride 间氯过氧苯甲酸 、 三苯基膦 、 锌 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.75h， 生成 (6R,6R',8R,8R')-(+)-5,5',6,6',7,7',8,8'-octahydro-6,6'7,7'-tetramethylbis(6,8-methanoquinoline) N-monoxide
  参考文献：
  名称：

  New Lewis-Basic N-Oxides as Chiral Organocatalysts in Asymmetric Allylation of Aldehydes

  摘要：

  Allylation of aromatic and heteroaromatic aldehydes 1a-k with allyltrichlorosilane 2 can be catalyzed by the new heterobidentate, terpene-derived bipyridine N-monoxides 4, 6a,b, and 8-11 (less than or equal to 10 mol %) to afford (S)-(-)-3 with high enantioselectivities (less than or equal to99% ee). The stereochemical outcome has been found to be controlled by the axial chirality of the catalyst, which in turn is determined by the central chirality of the annulated terpene units. Solvent effects on the conversion and the level of asymmetric induction have been elucidated, and MeCN has been identified as the optimal solvent for these catalysts.

  DOI：

  10.1021/jo035074i
• 作为产物：
  描述：

  beta-pinene 在 吡啶 、 sodium periodate 、 四氧化锇 、 十二/十四烷基二甲基氧化胺 、 盐酸羟胺 、 铁粉 、 溶剂黄146 、 三氯氧磷 作用下， 以 乙醇 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 3.17h， 生成 (6R,8R)-(-)-2-chloro-5,6,7,8,-tetrahydro-7,7-dimethyl-[6,8-methanoquinoline]
  参考文献：
  名称：

  PINDY:  A Novel, Pinene-Derived Bipyridine Ligand and Its Application in Asymmetric, Copper(I)-Catalyzed Allylic Oxidation

  摘要：

  [GRAPHICS]The title bipyridine ligand (+)-6(PINDY), prepared in five steps from (-)-beta-pinene, forms a stable complex with CuCl2 (8) that has been characterized by X-ray crystallography to reveal an unusual geometry at Cu. Triflate 9 proved to catalyze asymmetric allylic oxidation (10 --> 11; rt, similar to 30 min, 49-75% ee).

  DOI：

  10.1021/ol006111k

文献信息

• Hydrodehalogenation of halogenated pyridines and quinolines by sodium borohydride/N,N,N′,N′-tetramethylethylenediamine under palladium catalysis
  作者：Giorgio Chelucci

  DOI：10.1016/j.tetlet.2010.01.053

  日期：2010.3

  reported. Catalytic amounts of [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II) in combination with NaBH4–TMEDA rapidly hydrodehalogenate chloro(bromo)-pyridines and -quinolines at room temperature in quantitative yields. Chemoselective reduction of 4,7-dichloroquinoline affords 7-chloroquinoline as the sole product in almost quantitative yield. Moreover, palladium(II) acetate-triphenylphosphine

  据报道，在钯催化剂下，硼氢化钠/ N，N，N'，N'-四甲基乙二胺（NaBH 4 -TMEDA）体系可将卤代吡啶和喹啉进行加氢脱卤。催化量的[1,1 ' -双（二苯基膦基）二茂铁]在用NaBH组合二氯化钯（II）4 -TMEDA迅速hydrodehalogenate氯（溴）-pyridines并在定量产率室温-quinolines。化学选择性还原4,7-二氯喹啉可提供7-氯喹啉作为唯一产物，几乎定量地收率。此外，乙酸钯（II）-三苯膦和NaBH 4–TMEDA能够有效还原反应性溴吡啶和喹啉。
• Synthesis of C2-symmetric and unsymmetrically substituted 2,2′-dipyridylamines and crystal structure of a chiral 2,2′-dipyridylamine copper(II) complex
  作者：Carsten Bolm、Jean-Cédric Frison、Jacques Le Paih、Christian Moessner、Gerhard Raabe

  DOI：10.1016/j.jorganchem.2004.06.032

  日期：2004.11

  C2-symmetric and unsymmetrically substituted 2,2′-dipyridylamines have been synthesized by sequential Buchwald–Hartwig aminations of halo-pyridines. The X-ray crystal structure of a copper dichloride complex bearing a C2-symmetric 2,2′-dipyridylamine reveals details of the binding properties of the ligand and the coordination geometry at the metal center. In preliminary experiments the use of the new

  C 2对称和不对称取代的2,2'-联吡啶胺是通过卤代吡啶的连续布赫瓦尔德-哈特维希胺化合成的。带有C 2对称的2,2'-联吡啶胺的二氯化铜配合物的X射线晶体结构揭示了配体的结合性质和金属中心配位几何结构的细节。在初步实验中，已经证明了在不对称催化中使用新的氮螯合物。
• NaBH4-TMEDA and a palladium catalyst as efficient regio- and chemoselective system for the hydrodehalogenation of halogenated heterocycles
  作者：Giorgio Chelucci、Susanna Figus

  DOI：10.1016/j.molcata.2014.06.012

  日期：2014.11
• New Lewis-Basic <i>N</i>-Oxides as Chiral Organocatalysts in Asymmetric Allylation of Aldehydes
  作者：Andrei V. Malkov、Mark Bell、Monica Orsini、Daniele Pernazza、Antonio Massa、Pavel Herrmann、Premji Meghani、Pavel Kočovský

  DOI：10.1021/jo035074i

  日期：2003.12.1

  Allylation of aromatic and heteroaromatic aldehydes 1a-k with allyltrichlorosilane 2 can be catalyzed by the new heterobidentate, terpene-derived bipyridine N-monoxides 4, 6a,b, and 8-11 (less than or equal to 10 mol %) to afford (S)-(-)-3 with high enantioselectivities (less than or equal to99% ee). The stereochemical outcome has been found to be controlled by the axial chirality of the catalyst, which in turn is determined by the central chirality of the annulated terpene units. Solvent effects on the conversion and the level of asymmetric induction have been elucidated, and MeCN has been identified as the optimal solvent for these catalysts.
• PINDY:  A Novel, Pinene-Derived Bipyridine Ligand and Its Application in Asymmetric, Copper(I)-Catalyzed Allylic Oxidation
  作者：Andrei V. Malkov、Marco Bella、Vratislav Langer、Pavel Kočovský

  DOI：10.1021/ol006111k

  日期：2000.10.1

  [GRAPHICS]The title bipyridine ligand (+)-6(PINDY), prepared in five steps from (-)-beta-pinene, forms a stable complex with CuCl2 (8) that has been characterized by X-ray crystallography to reveal an unusual geometry at Cu. Triflate 9 proved to catalyze asymmetric allylic oxidation (10 --> 11; rt, similar to 30 min, 49-75% ee).