(2S)-2-((R)-hydroxy(4-nitrophenyl)methyl)cycloheptan-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S)-2-((R)-hydroxy(4-nitrophenyl)methyl)cycloheptan-1-one
• 英文别名: (S)-2-((R)-hydroxy(4-nitrophenyl)methyl)cycloheptanone；2-(hydroxy(4-nitrophenyl)methyl)cycloheptanone；(2S,1'R)-2-[1'-hydroxy-1'-(4-nitrophenyl)methyl]cycloheptan-1-one；(2S,1'R)-2-(hydroxy(p-nitrophenyl)methyl)cycloheptan-1-one；(2S)-2-[(R)-hydroxy-(4-nitrophenyl)methyl]cycloheptan-1-one
• 化学式: C₁₄H₁₇NO₄
• 分子量: 263.293
• InChiKey: XIYPQAZIVNVHJP-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S)-2-((R)-hydroxy(4-nitrophenyl)methyl)cycloheptan-1-one 在 吡啶 、 盐酸羟胺 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  通过[羟基（甲苯磺酰氧基）碘]苯（HTIB）介导的氧化性N-O偶联合成异恶唑啉N-氧化物

  摘要：

  描述了一种由HTIB介导的氧化性N-O偶联策略，用于从β-羟基酮肟合成某些异恶唑啉N-氧化物衍生物，以及对在两种不同溶剂中进行N-O偶联效率的比较研究。提出了一种可行的转换机制。

  DOI：

  10.1021/jo1018393
• 作为产物：
  描述：

  对硝基苯甲醛 、 环庚酮 在 (1R,2R)-N¹,N¹-dicyclopentylcyclohexane-1,2-diamine 、 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 24.08h， 以71%的产率得到(2S)-2-((R)-hydroxy(4-nitrophenyl)methyl)cycloheptan-1-one
  参考文献：
  名称：

  Highly stereoselective anti-aldol reactions catalyzed by simple chiral diamines and their unique application in configuration switch of aldol products

  摘要：

  Chiral derivatives of trans-1,2-diaminocyclohexane with different N,N-dialkyl groups in well-defined orientations have been synthesized, and applied as catalysts for the asymmetric aldol reaction between a variety of aldehydes and ketones. Enantiomeric catalyst 1j catalyzed the reaction in ethanol and provided excellent diastereoselectivity and enantioselectivity. Significantly, simple replacement of organic solvents with water switched the products of the aldol reactions from anti to syn configuration. Such catalytic reactions led to the products with anti to syn diastereoselectivity up to 99:1 in ethanol, while in water gave the products with syn to anti diastereoselectivity up to 99:1. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.09.053

文献信息

• Prolinamides of Aminouracils, Organocatalyst Modifiable by Complementary Modules
  作者：Karen M. Ruíz-Pérez、Beatriz Quiroz-García、Marcos Hernández-Rodríguez

  DOI：10.1002/ejoc.201800886

  日期：2018.11.8

  Prolinamide organocatalysts with aminouracils have the features of enhanced NH acidity, an additional hydrogen‐bond donor and the self‐assembly with complementary modules by Watson–Crick pairing. Each module affects the selectivity of the reaction and particularly 2,6‐diaminopyridine is beneficial to the selectivity in the reaction.

  带有氨基尿嘧啶的脯氨酰胺有机催化剂具有增强的NH酸度，额外的氢键供体以及通过沃森-克里克配对与互补模块自组装的特点。每个模块都会影响反应的选择性，特别是2,6-二氨基吡啶对反应的选择性有益。
• Highly enantioselective aldol reactions using a tropos dibenz[c,e]azepine organocatalyst
  作者：Barry Lygo、Christopher Davison、Timothy Evans、James A.R. Gilks、John Leonard、Claude-Eric Roy

  DOI：10.1016/j.tet.2011.09.101

  日期：2011.12

  The four-step synthesis of a chiral primary tertiary diamine salt, possessing a tropos dibenz[c,e]azepine ring is described. It is shown that 3.5–5 mol % of this salt is capable of promoting highly enantioselective crossed-aldol reactions between cyclohexanone and a series of aromatic aldehydes. In all cases, the aldol reactions proceed with high diastereoselectivity for the anti-aldol product. The

  描述了具有对位二苯并[ c，e ] a庚环的手性伯叔二胺盐的四步合成。结果表明，这种盐的3.5–5 mol％能够促进环己酮与一系列芳香醛之间的高度对映选择性的交叉羟醛反应。在所有情况下，羟醛缩合反应继续进行高非对映选择性的反-aldol产品。还描述了涉及其他环状酮和非环状酮的交叉醇醛缩合反应的结果。所有涉及环状酮的例子都会导致对抗羟醛产物的选择性，而发现非环状酮有利于合成-aldol产品。还讨论了手性伯叔二胺盐在醛醇缩合反应催化中的作用。
• Asymmetric Aldol Reaction Catalyzed by the Anion of an Ionic Liquid
  作者：Vincent Gauchot、Andreea R. Schmitzer

  DOI：10.1021/jo300737u

  日期：2012.6.1

  its applications as a catalyst for the asymmetric aldol reaction. By performing the aldol reaction in [Bmim]NTf2 as a solvent, we report excellent isolated yields of the aldol product (up to 99%), as well as modest to excellent selectivities (dr superior to 99:1. ee up to 89%). Mechanistic insights and the origins of the selectivity of the aldol reaction are discussed on the basis of the results obtained

  本文中，我们报道了衍生自反式-1-羟基脯氨酸的手性咪唑盐的合成及其作为不对称羟醛反应的催化剂的应用。通过在[Bmim] NTf 2中作为溶剂进行羟醛反应，我们报告了羟醛产物的优良分离产率（高达99％），以及中等至优异的选择性（dr优于99：1 ee高达89） ％）。基于两种具有不同氢键电势的​​催化咪唑盐获得的结果，讨论了机械学见解和醛醇缩合反应选择性的起源。
• 3,3′-Bithiophene-Based Chiral Bisphosphine Oxides as Organocatalysts in Silicon-Derived Lewis Acid Mediated Reactions
  作者：Sergio Rossi、Tiziana Benincori、Laura Maria Raimondi、Maurizio Benaglia

  DOI：10.1055/s-0039-1690777

  日期：2020.4

  This account summarizes the development of new biheteroaromatic chiral bisphosphine oxides. 3,3′-Bithiophene-based phosphine oxides (BITIOPOs) have been successfully used as organocatalysts to promote Lewis base catalyzed, Lewis acid mediated stereoselective transformations. These highly electron-rich compounds, in combination with trichorosilyl derivatives (allyltrichlorosilane and silicon tetrachloride)

  该帐户总结了新的双杂芳族手性双膦氧化物的开发。3,3'-联噻吩基氧化膦 (BITIOPO) 已成功用作有机催化剂，以促进路易斯碱催化、路易斯酸介导的立体选择性转化。这些高度富电子的化合物与三氯甲硅烷基衍生物（烯丙基三氯硅烷和四氯化硅）结合，生成高价硅物质，在高度非对映选择性和对映选择性有机反应中充当手性路易斯酸。详细讨论了与这些应用程序相关的几个相关示例。
• Different bio/Lewis acid-catalyzed stereoselective aldol reactions in various mediums
  作者：Tülay Yıldız、Hasniye Yaşa、Belma Hasdemir、Ayşe S. Yusufoğlu

  DOI：10.1007/s00706-017-1967-z

  日期：2017.8

  Brønsted acids were used for asymmetric aldol reactions of aromatic, heteroaromatic, cyclic, and acyclic six ketones and eleven aldehydes. Optimum reaction conditions were determined by changing temperature and enzyme, ketone, aldehyde, solvent, cofactors types, amounts, and ratios. PPL (porcine pancreatic lipase) of animal and AL-AN (amano lipase A from Aspergillus niger) of fungal origins were the

  摘要在这项工作中，八种不同的粗制生物催化剂与六种路易斯酸和三种布朗斯台德酸一起用于芳族，杂芳族，环状和无环六种酮和十一种醛的不对称羟醛反应。最佳反应条件是通过改变温度和酶，酮，醛，溶剂，辅因子的类型，数量和比例来确定的。动物的PPL（猪胰脂肪酶）和真菌来源的AL-AN（黑曲霉的天基脂肪酶A ）是最好的，并且相互比较。CoCl 2是最好的辅因子，与没有辅因子相比，它能更好地催化酶促醛缩反应。CoCl 2以前未用于酶促醛醇缩合反应。本研究中的方法使用粗制生物催化剂（PPL或AL-AN）和CoCl乙腈-水中的2被发现是不对称醛醇缩合反应的常规有用的生物催化方法，并且具有比文献中更好的ee值。 图形概要