cis-10-formylpinane

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: cis-10-formylpinane
• 英文别名: heptanyl-2>-acetaldehyd；2-[(1R,2R,5R)-6,6-dimethyl-2-bicyclo[3.1.1]heptanyl]acetaldehyde
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: AVQRHKZLVPSHIE-OPRDCNLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-10-formylpinane 在 chromium(VI) oxide 作用下， 以 吡啶 、 乙醚 为溶剂， 生成 heptanyl-2>-propanon-2
  参考文献：
  名称：

  Thermal Condensation of α-Keto Esters with Olefins

  摘要：

  DOI：

  10.1021/ja01505a029
• 作为产物：
  描述：

  (+)-cis-2-(6,6-dimethyl-bicyclo[3.1.1]hept-2-yl)-ethanol 在 chromium(VI) oxide 、 叔丁醇 作用下， 以 苯 为溶剂， 生成 cis-10-formylpinane
  参考文献：
  名称：

  Thermal Condensation of α-Keto Esters with Olefins

  摘要：

  DOI：

  10.1021/ja01505a029

文献信息

• Rhodium catalyzed hydroformylation of β-pinene and camphene: effect of phosphorous ligands and reaction conditions on diastereoselectivity
  作者：Humberto J.V. Barros、Maria L. Ospina、Eduardo Arguello、William R. Rocha、Elena V. Gusevskaya、Eduardo N. dos Santos

  DOI：10.1016/s0022-328x(03)00098-6

  日期：2003.4

  effect of phosphorus ligands on the rhodium catalyzed hydroformylation of β-pinene and camphene has been studied. In unmodified systems, β-pinene undergoes a fast isomerization to α-pinene. At longer reaction times and higher temperatures, the isomerization equilibrium is shifted resulting in the 80% chemoselectivity for β-pinene hydroformylation products (97% trans). The addition of various diphosphines

  研究了磷配体对铑催化β-pine烯和and烯的加氢甲酰化的影响。在未修饰的系统中，β-pine烯会快速异构化为α-pine烯。在更长的反应时间和更高的温度下，异构化平衡发生变化，导致β-pine烯加氢甲酰化产物的化学选择性达到80％（反式为97％）。各种二膦，膦或亚磷酸酯的添加可改善化学选择性并将加氢甲酰化反应转变为顺式醛3a。β-pine烯的加氢甲酰化反应的速率和非对映选择性都受辅助配体碱性的影响，但令人惊讶的是，对于锥角为128–165的配体，其立体特征与催化体系的非对映选择性之间没有相关性令人惊讶。 °。具有更多碱性配体的系统在β-pine烯加氢甲酰基化反应中显示出较低的活性，较高的非对映选择性和通常较高的化学选择性。在改性和​​未改性的体系中，systems烯都能生成线性醛6，几乎具有100％的区域选择性和化学选择性。磷配体的添加有利于内异构体6b：6a / 6b的形成≈1/ 1.
• Catalytic hydroformylation of (1S,5S)-(−)- and (1R,5R)-(+)-β-pinene: stereoselective synthesis and spectroscopic characterization of (1S,2R,5S)-, (1S,2S,5S)-, (1R,2R,5R)- and (1R,2S,5R)-10-formylpinane
  作者：Fabrizio Azzaroni、Paolo Biscarini、Silvia Bordoni、Giuliano Longoni、Emanuela Venturini

  DOI：10.1016/0022-328x(95)05778-n

  日期：1996.2

  (1S,5S)-(−)- and (1R,5R)-(+)-β-pinene have been hydroformylated in toluene to give (1S,2R,5S)- and (1R,2S,5R)-10-formylpinane with up to 95% diastereoselectivity using bimetallic CoRh(CO)7 as a catalyst; the latter was generated in situ from preformed Co2Rh2(CO)12 or a stoichiometric mixture of either [Rh4(CO)12] or [Rh6(CO)16] and [Co2(CO)8]. At 70–125°C and under 60 atm of syngas, the yields of hydroformylated

  （1 S，5 S）-（-）-和（1 R，5 R）-（+）- β- pine烯已在甲苯中加氢甲酰化，得到（1 S，2 R，5 S）-和（1 R使用双金属CoRh（CO）7作为催化剂，具有高达95％的非对映选择性的，2 S，5 R）-10-甲酰基pin烷; 后者由预制的Co 2 Rh 2（CO）12或[Rh 4（CO）12 ]或[Rh 6（CO）16 ]和[Co 2（CO）8 ]。在70–125°C和60atm的合成气下，加氢甲酰化产物的收率不会超过30％，这是因为β-pine烯会同时异构化为α-pine烯。在所有情况下，催化剂都是以可溶性羰基钴衍生物和包含大部分铑（主要为[Rh 6（CO）16 ] ）的晶体沉淀物的混合物形式回收的。通过在四氢呋喃中与作为催化剂前体的[Rh 4（CO）12 ]和[N（PPh 3）2 ] Cl的混合物进行反应，可获得相当的收率和非对映选择性。
• Cationic rhodium(I) complexes containing 4,4′-disubstituted 2,2′-bipyridines: A systematic variation on electron density over the metal centre
  作者：Paulo E.A. Ribeiro、Claudio L. Donnici、Eduardo N. dos Santos

  DOI：10.1016/j.jorganchem.2005.12.049

  日期：2006.4

  A series of [Rh(COD)(X-2-bipy)]BF4 complexes (COD = 1,5-cyclooctadiene; X-2-bipy = 4,4'-disubstituted 2,2'-bipyridines; X = OCH3, CH3, H, Cl or NO2) has been prepared from [Rh(COD)Cl](2). The complexes for X = OCH3, Cl and NO2 have not been described previously in the literature. All complexes have been characterised by elemental analysis, IR, H-1 NMR and UV-Vis spectrometry. This series of complexes presents a wide variation on electron density over the metal centre with virtually no variation on its steric environment which discloses interesting possibilities for catalytic and electro-catalytic studies. A preliminary evaluation of these complexes on the hydroformylation of camphene and beta-pinene showed that under the rather drastic conditions employed the complexes acted as a precursor for (Rh(CO)(3)H], which accounts for most of the catalytic activity. (c) 2006 Elsevier B.V. All rights reserved.
• Thermal Condensation of α-Keto Esters with Olefins
  作者：R. T. Arnold、P. Veeravagu

  DOI：10.1021/ja01505a029

  日期：1960.10