[(1S,2R)-trans-2-(quinolin-2-yl)cyclohexan-1-oxy]diphenyl phosphine | 1334808-86-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: [(1S,2R)-trans-2-(quinolin-2-yl)cyclohexan-1-oxy]diphenyl phosphine
• 英文别名: [(1S,2R)-trans-2-(quinolin-2-yl)cyclohexan-1-oxy]diphenylphosphine
• CAS: 1334808-86-4
• 化学式: C₂₇H₂₆NOP
• 分子量: 411.483
• InChiKey: IIDDFDNAGUOLSE-SQHAQQRYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  30.0
• 可旋转键数：
  5.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  22.12
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 [(1S,2R)-trans-2-(quinolin-2-yl)cyclohexan-1-oxy]diphenyl phosphine 、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以81%的产率得到
  参考文献：
  名称：

  Improved Synthesis of Cyclohexane-Backbone Iridium-Complexes of Quinoline-Phosphine and Their Applications in Asymmetric Hydrogenation

  摘要：

  The iridium-complexes 3 and 4 with cyclohexane-backbone derived from quinoline were easily synthesized. The key step is cis/trans stereoselective reduction of 2-(quinolin-2-yl)cyclohexanone 5 to trans-2-(quinolin-2-yl)cyclohexanol 6 using Al(Oi-Pr)(3)/i-PrOH and the following diastereomeric optical resolution of racemic 6 using 0.50 equiv (S)-mandelic acid in EtOAc. These complexes were used in the asymmetric hydrogenation of (E)-1,2-diphenylpropene with up to 13% ee/48% cony. using 3 and 35% ee/9% cony. using 4. For the hydrogenation of (2H-chromen-3-yl)methanol, up to 80% ee/95% yield and 72% ee/96% yield were achieved. The same configuration of the products by using 3 and 4 suggested that the absolute configuration was controlled by the configuration of the stereogenic quinolinyl-bearing carbon of the complexes.

  DOI：

  10.3987/com-20-14284
• 作为产物：
  描述：

  trans-(2-hydroxycyclohexyl)quinoline 在 (S)-(+)-扁桃酸 、 三乙胺 、 4,5-二氯咪唑 作用下， 以 乙酸乙酯 、 1,2-二氯乙烷 为溶剂， 反应 6.0h， 生成 [(1S,2R)-trans-2-(quinolin-2-yl)cyclohexan-1-oxy]diphenyl phosphine
  参考文献：
  名称：

  Improved Synthesis of Cyclohexane-Backbone Iridium-Complexes of Quinoline-Phosphine and Their Applications in Asymmetric Hydrogenation

  摘要：

  The iridium-complexes 3 and 4 with cyclohexane-backbone derived from quinoline were easily synthesized. The key step is cis/trans stereoselective reduction of 2-(quinolin-2-yl)cyclohexanone 5 to trans-2-(quinolin-2-yl)cyclohexanol 6 using Al(Oi-Pr)(3)/i-PrOH and the following diastereomeric optical resolution of racemic 6 using 0.50 equiv (S)-mandelic acid in EtOAc. These complexes were used in the asymmetric hydrogenation of (E)-1,2-diphenylpropene with up to 13% ee/48% cony. using 3 and 35% ee/9% cony. using 4. For the hydrogenation of (2H-chromen-3-yl)methanol, up to 80% ee/95% yield and 72% ee/96% yield were achieved. The same configuration of the products by using 3 and 4 suggested that the absolute configuration was controlled by the configuration of the stereogenic quinolinyl-bearing carbon of the complexes.

  DOI：

  10.3987/com-20-14284

文献信息

• Synthesis of Chiral P,N-ligands derived from Quinoline and their Application in Asymmetric Allylic Alkylations
  作者：Yan-Hong Shen、Hui-Chao Lv、Liang Zhao

  DOI：10.3184/174751911x13082269792294

  日期：2011.6

  Chiral P,N-ligands derived from quinoline and with a trans and cis cyclohexane backbone were easily synthesised in four steps from quinoline N-oxide. The enantiopure trans isomer was obtained by the way of chiral resolution of the mixture of trans- and cis-2-(quinolin-2-yl)cyclohexanol with dibenzoyltartaric acid and then subjected to a Mitsunobu reaction and deprotection to give the corresponding

  从喹啉衍生的具有反式和顺式环己烷主链的手性 P,N-配体可以通过四步从喹啉 N-氧化物轻松合成。反式和顺式-2-(喹啉-2-基)环己醇与二苯甲酰酒石酸的混合物经手性拆分，经光延反应脱保护得到相应的顺式异构体，得到对映体纯反式异构体。光学纯的反式和顺式异构体与氯二苯膦或 PAr2NEt2 反应得到反式和顺式 P,N-配体，它们分别用于不对称烯丙基烷基化，ee 和 ee 分别高达 78% 和 84%。