(6R,6R',8R,8R')-(+)-5,5',6,6',7,7',8,8'-octahydro-6,6'7,7'-tetramethylbis(6,8-methanoquinoline) N-monoxide

• 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,6R',8R,8R')-(+)-5,5',6,6',7,7',8,8'-octahydro-6,6'7,7'-tetramethylbis(6,8-methanoquinoline) N-monoxide
• 英文别名: (+)-PINDOX；(1R,9R)-4-[(1R,9R)-10,10-dimethyl-3-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-4-yl]-10,10-dimethyl-3-oxido-3-azoniatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• 化学式: C₂₄H₂₈N₂O
• 分子量: 360.499
• InChiKey: AJEWIMQJWYDMIN-XSLAGTTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  38.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1R,5S)-6,6-Dimethyl-bicyclo[3.1.1]heptan-2-one oxime 在 nickel dichloride 铁粉 、 溶剂黄146 、 间氯过氧苯甲酸 、 三苯基膦 、 锌 、 三氯氧磷 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.92h， 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
• 作为试剂：
  描述：

  丙烯基三氯硅烷 、 1-萘甲醛 在 四丁基碘化铵 、 N,N-二异丙基乙胺 、 (6R,6R',8R,8R')-(+)-5,5',6,6',7,7',8,8'-octahydro-6,6'7,7'-tetramethylbis(6,8-methanoquinoline) N-monoxide 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 (R)-1-naphthalen-1-yl-but-3-en-1-ol 、 (S)-1-(1-naphthyl)-3-buten-1-ol
  参考文献：
  名称：

  手性2,2'-联吡啶型N-一氧化氮作为醛与烯丙基三氯硅烷的对映选择性烯丙基化的有机催化剂。

  摘要：

  [反应：见正文]芳香族和杂芳族醛的Sakurai-Hosomi型烯丙基化反应可以通过具有高对映选择性的新型杂双酸二联吡啶一氧化物PINDOX来催化。立体化学结果主要由PINDOX中的轴向手性控制，而轴向手性又由环戊烯单元确定。

  DOI：

  10.1021/ol025654m

文献信息

• Chiral 2,2‘-Bipyridine-Type <i>N</i>-Monoxides as Organocatalysts in the Enantioselective Allylation of Aldehydes with Allyltrichlorosilane
  作者：Andrei V. Malkov、Monica Orsini、Daniele Pernazza、Ken W. Muir、Vratislav Langer、Premji Meghani、Pavel Kočovský

  DOI：10.1021/ol025654m

  日期：2002.3.1

  [reaction: see text] The Sakurai-Hosomi-type allylation of aromatic and heteroaromatic aldehydes can be catalyzed by the new heterobidenate bipyridine monoxide PINDOX with high enantioselectivities. The sterochemical outcome is mainly controlled by the axial chirality in PINDOX, which in turn is determined by the annulated terpene units.

  [反应：见正文]芳香族和杂芳族醛的Sakurai-Hosomi型烯丙基化反应可以通过具有高对映选择性的新型杂双酸二联吡啶一氧化物PINDOX来催化。立体化学结果主要由PINDOX中的轴向手性控制，而轴向手性又由环戊烯单元确定。
• 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.