(1R,2R,4R)-2-exo-hydroxy-2-endo-(pyridin-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptane | 100993-02-0

• 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: (1R,2R,4R)-2-exo-hydroxy-2-endo-(pyridin-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptane
• 英文别名: (1R,2R,4R)-1,7,7-trimethyl-2-(2'-pyridinyl)bicyclo[2.2.1]heptane-2-ol；(1R,2R,4R)-1,7,7-trimethyl-2-(2'-pyridinyl)bicyclo[2.2.1]heptan-2-ol；(1R,2R,4R)-1,7,7-trimethyl-2-(2'-pyridyl)bicyclo[2.2.1]heptan-2-ol；Bicyclo[2.2.1]heptan-2-ol, 1,7,7-trimethyl-2-(2-pyridinyl)-, (1R,2R,4R)-；(1R,2R,4R)-1,7,7-trimethyl-2-pyridin-2-ylbicyclo[2.2.1]heptan-2-ol
• CAS: 100993-02-0
• 化学式: C₁₅H₂₁NO
• 分子量: 231.338
• InChiKey: WUPYCTDTAKFJQT-DFBGVHRSSA-N

物化性质

• 沸点：
  342.9±17.0 °C(Predicted)
• 密度：
  1.095±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  33.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R,4R)-2-exo-hydroxy-2-endo-(pyridin-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptane 在 sodium hydride 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 39.5h， 生成 (1R,2S,3R,4S)-3-exo-phenylthio-2-endo-(2-pyridinyl)-1,7,7-trimethylbicyclo[2.2.1]heptane
  参考文献：
  名称：

  Enantiomerically pure pyridine and 2,2′-bipyridine thioethers: new N–S chiral ligands for asymmetric catalysis. Palladium-catalyzed allylic alkylation

  摘要：

  Diastereomeric pure pyridine and 2,2'-bipyridine thioethers, derived from (+)-camphor, were prepared and assessed in the enantioselective palladium-catalyzed allylic substitution of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate. Enantioselectivities of up to 76% were obtained. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00352-3
• 作为产物：
  描述：

  2-吡啶基锂 、 白樟油 在 cerium(III) chloride 作用下， 生成 (1R,2R,4R)-2-exo-hydroxy-2-endo-(pyridin-2-yl)-1,7,7-trimethylbicyclo[2.2.1]heptane
  参考文献：
  名称：

  从（+）-樟脑和（-）-杏仁酮一步合成高度光学选择性的新型旋光性氨基醇

  摘要：

  从CeCl 3活化的（+）-樟脑脂和（-）-甲ench酮以及N-官能化的有机锂化合物制备了新的旋光氨基醇。所获得的氨基醇以高收率和高达64％的对映选择性催化将二乙基锌添加到苯甲醛中。

  DOI：

  10.1016/s0957-4166(97)00182-1

文献信息

• Chiral bis(oxazoline) and pyridyl alcoholate dioxo-molybdenum(VI) complexes: synthesis, characterization and catalytic examinations
  作者：Fritz E Kühn*、Ana M Santos、André D Lopes、Isabel S Gonçalves、José E Rodrı́guez-Borges、Martyn Pillinger、Carlos C Romão*

  DOI：10.1016/s0022-328x(00)00774-9

  日期：2001.3

  with one or two equivalents of chiral ligand. Optically active aminoalcohols (L*) were obtained by reaction of the appropriate organolithium compound with (−)-menthone, (+)-8-phenylisomenthone, (−)-8-phenylmenthone, (+)-camphor and (−)-thujone. The molybdenum complexes were characterized by multinuclear NMR (1H, 13C, 17O, 95Mo) spectroscopy, IR spectroscopy and elemental analysis. 95Mo-NMR data reflected

  一组包含MoO 2 Cl 2 L **，MoO 2 Cl（THF）L *和MoO 2 L 2 *的手性钼（VI）配合物[L ** =手性双（恶唑啉），L * =手性2'-通过使溶剂取代的配合物MoO 2 Cl 2（THF）2与一或两个当量的手性配体反应，以高收率制备[吡啶基醇酸酯] 。旋光氨基醇（L *）是通过适当的有机锂化合物与（-）-薄荷酮，（+）-8-苯基异薄荷酮，（-）-8-苯基薄荷酮，（+）-樟脑和（-）-丁酮的反应获得的。钼配合物的特征在于多核NMR（1 H，13 C，17 O，95 Mo）光谱，IR光谱和元素分析。95 Mo-NMR数据反映了有机配体的供体能力，而1 H-NMR和IR数据对路易斯碱配体的变化相对无动于衷。评价该配合物作为叔酸反式-β-甲基苯乙烯不对称环氧化的催化剂丁基过氧化氢。双（恶唑啉）配合物显示出良好的催化活性，但光学收率低。MoO 2 Cl（THF）L *（L
• Chiral molybdenum(VI) and tungsten(VI) 2′-pyridinyl alcoholate complexes. Synthesis, structure and catalytic properties in asymmetric olefin epoxidation
  作者：Wolfgang A Herrmann、Joachim J Haider、Jörg Fridgen、Gerhard M Lobmaier、Michael Spiegler

  DOI：10.1016/s0022-328x(00)00112-1

  日期：2000.5

  chiral molybdenum(VI) and tungsten(VI) complexes of the type MO2L*2 (M=Mo, W; L*=chiral 2′-pyridinyl alcoholate), available through several synthetic pathways, and their catalytic behavior in the asymmetric epoxidation of unfunctionalized olefins are reported. MO2Cl2, MO2(acac)2, and Na2[MO4] (M=Mo, W) served as starting materials for the synthesis of the chiral molybdenum(VI) or tungsten(VI) complexes

  可通过几种合成途径获得的一类新的类型为MO 2 L * 2（M = MO，W; L * =手性2'-吡啶醇）的手性钼（VI）和钨（VI）配合物报道了未官能化烯烃在不对称环氧化中的行为。MO 2 Cl 2，MO 2（acac）2和Na 2 [MO 4]（M = MO，W）分别用作合成手性钼（VI）或钨（VI）配合物的原料。包括X射线晶体学分析在内，对新的oxo配合物进行了全面表征。手性2'-吡啶基醇酸酯配体衍生自（-）-薄荷酮，（-）-甲酮，（-）-樟脑或（+）-樟脑。为了在对映选择性环氧化中进行催化运行，将反式-甲基苯乙烯用作模型底物，将叔丁基氢过氧化物用作氧化剂。钼配合物表现出良好的催化活性和明显的光诱导作用。相比之下，类似的钨络合物在相当的光学产率下具有较低的活性。
• Method for isomerizing allyl alcohols
  申请人：Haese Frank

  公开号：US20050101807A1

  公开（公告）日：2005-05-12

  The present invention relates to a process for isomerizing reactant allyl alcohols of the formula (I) to product allyl alcohols of the general formula (II) where R1 to R5 are each hydrogen or a mono- or polyunsaturated or saturated C 1 -C 12 -alkyl radical, which can be substituted or unsubstituted, in both directions of the equilibrium, which comprises isomerizing in the presence of a dioxotungsten(VI) complex of the general formula (III), where L 1 , L 2 are each independently a ligand selected from the group consisting of the aminoalcohols, the aminophenols and mixtures thereof, m, n are each 1 or 2, new dioxotungsten(VI) complexes, and also their use.

  本发明涉及一种将式(I)的反应物烯丙基醇异构化为通式(II)的产物烯丙基醇的工艺 其中 R1 至 R5 分别为氢或单一或多元不饱和或饱和 C 1 -C 12 -烷基，可以是取代或未取代的、 在平衡的两个方向上，包括在通式(III)的二噁钨(VI)络合物存在下进行异构化、 其中 L 1 , L 2 各自独立地为一种配体，该配体选自由氨基醇、氨基苯酚及其混合物组成的组，m、n 各自为 1 或 2。
• Chiral 2-pyridyl alcoholate copper complexes: crystal structures of [bis(2-pyridyl alcoholate)copper(II)] and the use of [(2-pyridyl alcoholate)copper(II)]+and [(2-pyridyl alcoholate)copper(I)] in asymmetric cyclopropanation of styene and allylic oxidation of cyclohexene
  作者：Wing-Sze Lee、Hon-Kit Leung、Leung-Shi Cheng、Lai-Yuen Ng、Chi-Sing Lee、Ka-Hung Huang、Wing-Tak Wong、Hoi-Lun Kwong

  DOI：10.1016/j.ica.2004.06.043

  日期：2004.12

  Chiral N,O pyridine alcohols HL1-HL6 were used to form complexes with copper(II) ions. Ligands HL1 and HL2 formed complexes with copper(II) ions when Cu(OAc)(2) and HL were refluxed in methanol/ethanol mixture. Ligand HL3 formed a complex with copper(II) when deprotonated with NaH and stirred in a Cu(II) acetate THF solution. Ligands HL4-HL6 did not form complexes with copper(II) under similar conditions. Two complexes, [Cu(L-1)(2)] and [Cu(L-2)(2)], were isolated as single crystals and characterized by X-ray crystallography. These complexes showed low catalytic activities in asymmetric reactions. However, they became active when reacted with triflic acid. Copper complexes, [Cu(L)] or [Cu(L)](+), formed in situ by reacting ligands HL with copper(I) or (II) ions, respectively. were also found to be active copper catalysts for asymmetric cyclopropanation of styrene with ethyl diazoacetate and allylic oxidation of cyclohexene with t-butylperoxybenzoate. Enantioselectivities up to 56% and 38% were obtained in asymmetric cyclopropanation of styrene and asymmetric allylic oxidation of cyclohexene, respectively. (C) 2004 Elsevier B.V. All rights reserved.
• EP1455934B1
  申请人：——

  公开号：EP1455934B1

  公开（公告）日：2008-11-19