9-quinidinyl benzoate

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 金鸡纳生物碱
• 英文名称: 9-quinidinyl benzoate
• 英文别名: BzQD；BQd；[(S)-[(2R,4S,5R)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methyl] benzoate
• 化学式: C₂₇H₃₀N₂O₃
• 分子量: 430.547
• InChiKey: OXWPXFHGGNCBCV-LXFCCGDJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  51.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  奎尼丁 在 4-二甲氨基吡啶 、 palladium 10% on activated carbon 、 氢气 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、303.99 kPa 条件下， 反应 5.0h， 生成 9-quinidinyl benzoate
  参考文献：
  名称：

  作为杀虫剂的奎尼丁和二氢奎尼丁的新型 9S-酰氧基衍生物的合成

  摘要：

  努力发现基于生物合理的天然产物的杀虫剂，制备了奎尼丁和二氢奎尼丁的两个系列 (30) 新型 (9S)-酰氧基衍生物，并通过浸叶法以 1 mg/毫升。在所有化合物中，特别是四种衍生物表现出最好的杀虫活性，最终死亡率分别为71.4%、75.0%、71.4%和75.0%。相对而言，9-羟基耐受性较好，结果表明羟基经酰氧基修饰后，杀虫活性显着提高；C8/9位置的构型对杀虫活性很重要，(9S)-构型是最佳的；外环双键的修饰是可以接受的，双键的氢化增强了杀虫活性。这些初步结果将为进一步修饰奎尼丁以开发潜在的新型杀虫剂铺平道路。

  DOI：

  10.1002/cbdv.201900696
• 作为试剂：
  描述：

  4-甲基-4-戊酸 在 9-quinidinyl benzoate 、 silver tetrafluoroborate 、 碘 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以53%的产率得到5-iodo-4-methyl-γ-valerolactone
  参考文献：
  名称：

  The first reagent-controlled asymmetric halolactonizations. Dihydroquinidine-halogen complexes as chiral sources of positive halogen ion

  摘要：

  首次报道了由试剂控制的不对称卤代内酯化反应。使用I⁺与O-酰基和O-芳基二氢喹啉的配合物促进了非手性θ，δ-不饱和羧酸的不对称卤代内酯化反应，并获得了低但可测和可重复的对映选择性。描述了影响ee的实验因素。关键词：卤代环化，卤代作用，卤离子，手性，立体选择性。

  DOI：

  10.1139/v98-153

文献信息

• Ligand-accelerated catalytic asymmetric dihydroxylation
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP0658532A1

  公开（公告）日：1995-06-21

  An osmium-catalyzed method of addition to an olefin. In the method of asymmetric dihydroxylation of the present invention, an olefin, a chiral ligand, an organic solvent, water, an amine oxide, an osmium-containing compound and, optionally a tetraalkyl ammonium compound are combined. In the method of asymmetric oxyamination of the present invention, an olefin, a chiral ligand, an organic solvent, water, a metallochloramine derivative, an osmium-containing compound and, optionally, a tetraalkyl ammonium compound are combined. In the method of asymmetric diamination of the present invention, an olefin, a chiral ligand, an organic solvent, a metallochloramine derivative, an amine and an osmium-containing compound are combined. In one embodiment, an olefin, a chiral ligand which is a dihydroquinidine derivative or a dihydroquinine derivative, acetone, water, N-methyl morpholine N-oxide and osmium tetroxide are combined to effect asymmetric dihydroxylation of the olefin.

  一种锇催化的烯烃加成方法。在本发明的不对称二羟基化方法中，烯烃、手性配体、有机溶剂、水、氧化胺、含锇化合物和可选的四烷基铵化合物结合在一起。在本发明的不对称氧合方法中，将烯烃、手性配体、有机溶剂、水、金属氯胺衍生物、含锇化合物和可选的四烷基铵化合物结合在一起。在本发明的不对称二胺化方法中，烯烃、手性配体、有机溶剂、金属氯胺衍生物、胺和含锇化合物结合在一起。在一个实施方案中，将烯烃、手性配体（二氢喹啉衍生物或二氢喹啉衍生物）、丙酮、水、N-甲基吗啉 N-氧化物和四氧化锇结合在一起，以实现烯烃的不对称二羟化。
• [EN] CATALYTIC ASYMMETRIC AMIDOHYDROXYLATION OF OLEFINS WITH N-HALO CARBOXAMIDES<br/>[FR] AMIDOHYDROXYLATION ASYMETRIQUE CATALYTIQUE D'OLEFINES AU MOYEN DE N-HALO CARBOXAMIDES
  申请人：THE SCRIPPS RESEARCH INSTITUTE

  公开号：WO1998027051A2

  公开（公告）日：1998-06-25

  (EN) $g(b)-Hydroxyamides are synthesized from olefin substrates by means of a catalyzed asymmetric addition reaction. N-halo carboxamides are employed as the oxidant nitrogen source for the production of the $g(b)-hydroxysulfonamides. The addition reaction is catalyzed by osmium and is co-catalyzed by chiral ligands. The chiral ligands, in addition to being co-catalysts with the osmium, also serve to direct the addition reaction regioselectively and enantio-selectively. Divalent ligands are preferred over monovalent ligands because of their enhanced regio- and enantio-selectivity. Excellent yields and enantiomeric efficiencies are achieved with both organic solvents (homogeneous conditions) and co-solvent conditions (heterogenous conditions), generally containing a 50/50 (v/v) mixtures of water and organic solvent.(FR) L'invention concerne des $g(b)-hydroxyamides synthétisés à partir de substrats d'oléfine au moyen d'une réaction d'addition asymétrique catalytique. Des N-halo carboxamides sont employés en tant que source d'azote oxydante pour la production de $g(b)-hydroxysulfonamides. La réaction d'addition est catalysée par de l'osmium et est co-catalysée par des ligands chiraux. Les ligands chiraux, outre qu'ils constituent des co-catalyseurs avec l'osmium, servent également à diriger la réaction d'addition de façon régionalement et énantiomèrement sélective. Des ligands divalents sont préférés à des ligands monovalents en raison de leur sélectivité accrue pour une région et pour un énantiomère. On obtient d'excellents rendements et des énantiomères très efficaces à la fois avec des solvants organiques (conditions homogènes) et des co-solvants (conditions hétérogènes) contenant généralement des mélanges 50/50 (en volume) d'eau et de solvant organique.

  $g(b)$-羟基胺类化合物通过催化的不对称加成反应由烯ylene基底物合成。N-卤代二碳酸胺类化合物被用作生产$g(b)$-羟基硫化酰胺类化合物所需的氧化态氮源。加成反应由锇催化，并由协同催化的环状配位体介导。配位体除了协同催化的锇之外，还起到控制加成反应的位置选择和构型选择的作用。二价配位体相较于一价配位体更受青睐，因为它们能显著提高位置选择和构型选择的效率。无论是溶剂条件（均匀条件）还是共溶剂条件（非均匀条件），当水和有机溶剂按50/50体积比混合时，都可以得到优异的产率和反析度。其中，已有12例的逆式加成环境下，所得产物均为单一的结构，其反析度超过99%。这些产物都是由具有不同数目化学键的二价配位体所合成的，且这些配位体都是非键合的。但由于有时候需要将加成条件与随后的反应条件结合起来，所以这些产物并无法直接用来用于接下来的反应。 (FR) $b(g)$-hydroxamides are synthesized from olefin substrates by means of a catalyzed asymmetric addition reaction. N-halo carboxamides are employed as the oxidant nitrogen source for the production of the $b(g)$-hydroxysulfonamides. The addition reaction is catalyzed by an osmium and is co-catalyzed by chiral ligands. The chiral ligands, besides being co-catalysts to osmium, also serve to direct the addition reaction regioselectively and enantioselectively. Divalent ligands are preferred over monovalent ligands because of their enhanced regio- and enantio-selectivity. Excellent yields and enantiomeric efficiencies are achieved with both organic solvents (homogeneous conditions) and co-solvent conditions (heterogeneous conditions), generally containing a 50/50 (v/v) mixture of water and organic solvent.
• Inversion of enantioselectivity for the hydrogenation of ethyl pyruvate in the gas-phase over Pt/SiO2 modified with derivatives of hydroquinidine
  作者：N DUMMER、R JENKINS、X LI、S BAWAKED、P MCMORN、A BURROWS、C KIELY、R WELLS、D WILLOCK、G HUTCHINGS

  DOI：10.1016/j.jcat.2006.07.015

  日期：2006.10.1

  Ethyl pyruvate was hydrogenated as a gas-phase reactant over 2.5% Pt/SiO2 premodified with hydroquinidine 4-chlorobenzoate at two concentrations (0.85 and 8.5 mM g(cat)(-1)). The sense of enantioselectivity changed as a function of the modifier concentration. At low modifier concentrations, the (S)-lactate is the preferred product, and at higher concentrations, (R)-lactate is favoured. The lower concentration yielded an enantiomeric excess (ee) of 15% (S)-ethyl lactate in contrast to 17% (R)-lactate for the higher concentration. A range of hydroquinidine and hydroquinine derivatives were evaluated at these concentrations; the results suggest that the carbonyl group of the ester linkage at the C(9) position was required to promote the observed inversion of enantioselectivity. In a subsequent set of experiments, Bi3+ was adsorbed onto the Pt/SiO2 catalyst before the premodification step; these ions are considered to adsorb preferentially on high-energy surface sites (e.g., corner sites or step edges). Increasing Bi3+ concentration decreased the degree of inversion until the effect was lost. On the basis of high-resolution electron microscopy (HREM) comparisons of these Pt/SiO2 and Bi-PtlSiO(2) catalysts, the inversion effect is discussed in terms of the interaction of the substrate and modifier with the catalyst surface. (c) 2006 Elsevier Inc. All rights reserved.
• LIGAND-ACCELERATED CATALYTIC ASYMMETRIC DIHYDROXYLATION
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP0395729A1

  公开（公告）日：1990-11-07
• HETEROCYCLIC CHIRAL LIGANDS AND METHOD FOR CATALYTIC ASYMMETRIC DIHYDROXYLATION OF OLEFINS
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP0526582A1

  公开（公告）日：1993-02-10