(S)-2-((S)-2-nitro-1-phenylethyl)cyclohexanone | 84025-87-6

• 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: (S)-2-((S)-2-nitro-1-phenylethyl)cyclohexanone
• 英文别名: (2S)-2-[(1S)-2-nitro-1-phenylethyl]cyclohexan-1-one
• CAS: 84025-87-6
• 化学式: C₁₄H₁₇NO₃
• 分子量: 247.294
• InChiKey: STOOUUNOLPMRGC-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-环己烯氧基三甲基硅烷 在 potassium fluoride 二异丙氧基二氯化钛 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (S)-2-((S)-2-nitro-1-phenylethyl)cyclohexanone
  参考文献：
  名称：

  通过使用1-（三甲基甲硅烷氧基）环己烯/二氯（二异丙氧基）钛将环己酮迈克尔加成至β-硝基苯乙烯的逆立体化学过程。初步沟通

  摘要：

  由化学计量过量的二氯（二异丙氧基）钛，1-（三甲基甲硅烷氧基）环己烯和对位取代的β-硝基苯乙烯（Y = H，CH 3，CH 3 O，CN）于-90°在CH 2 Cl 2溶液中合并优先考虑相对话题性ul –与烯醇盐或烯胺的相应反应相反。主要产物是可分离的双环硝酸盐3-5，可通过KF在MeOH中裂解，得到芳基（硝基乙基）取代的环己酮1和2（表1和2，给出了两个典型的过程）。主要产物（2∶1至4∶1）是迄今尚不容易获得的1-构型的非对映异构体2。代替溶剂化，双环硝酸盐5可用于硝基羟醛加成（6）和[3 + 2]-偶极环加成（7），用于非对映选择性地提供具有4个不对称C原子的产品（不包括缩醛中心）。该迈克尔加成这里描述是又一个的另一示例UL诱导三角中心的结合-路易斯酸，重写供体组件的配置的影响。

  DOI：

  10.1002/hlca.19850680205

文献信息

• 4-Aminothioureaprolinal Dithioacetal as a Catalyst for Highly Enantioselective Michael Additions of Ketones and Aldehydes to Nitroolefins
  作者：Yong-Ming Chuan、Li-Yang Yin、Yan-Mei Zhang、Yun-Gui Peng

  DOI：10.1002/ejoc.201001211

  日期：2011.1

  4-Aminothioureaprolinal dithioacetal 4a is a highly efficient catalyst for the asymmetric Michael addition of ketones and aldehydes to nitroolefins requiring only 3 mol-% catalyst loading. The reactions proceeded smoothly and gave syn selective adducts with excellent yields (up to 98 % yield), diastereoselectivity (up to >99:1 dr), and enantioselectivity (up to 99 % ee) under solvent free conditions

  4-Aminothioureaprolinal dithioacetal 4a 是一种高效催化剂，用于酮和醛与硝基烯烃的不对称迈克尔加成反应，仅需 3 mol% 的催化剂负载。在室温下无溶剂条件下，反应顺利进行，得到顺式选择性加合物，产率高（产率高达 98%）、非对映选择性（高达 >99:1 dr）和对映选择性（高达 99% ee）。这种极其简单实用的程序增加了该反应的吸引力。
• Asymmetric Michael Addition Induced by the Anion of an Imidazolium Salt
  作者：Vincent Gauchot、Julien Gravel、Andreea R. Schmitzer

  DOI：10.1002/ejoc.201201068

  日期：2012.11

  We describe the application of a chiral catalytic imidazolium salt derived from trans-L-hydroxyproline, the anion being the catalytic entity, as a catalyst for the asymmetric Michael addition. We report the first example of a catalytic Michael addition using this type of catalyst, leading to excellent yields (up to 99 %) and good selectivities (up to 99:1 dr, up to 82 % ee).

  我们描述了衍生自反式-L-羟脯氨酸的手性催化咪唑盐的应用，阴离子是催化实体，作为不对称迈克尔加成的催化剂。我们报告了使用此类催化剂的催化迈克尔加成的第一个例子，导致优异的产率（高达 99%）和良好的选择性（高达 99:1 dr，高达 82% ee）。
• C₂ -symmetric sulfonamides as homogeneous and heterogeneous organocatalysts that mimic enzymes in enantioselective Michael additions
  作者：Harold Cruz、Felipe A. Servín、Domingo Madrigal、Daniel Chávez、Sergio Perez-Sicairos、Gerardo Aguirre、Andrew L. Cooksy、Ratnasamy Somanathan

  DOI：10.1002/chir.22984

  日期：2018.8

  homogeneous and heterogeneous organocatalysts and their application in the enantioselective conjugate 1,4‐Michael addition of carbonylic nucleophiles to β‐nitrostyrene. Organocatalysts hydrogen bond to β‐nitrostyrene and enamine in the transition state, mimicking an enzyme leading to final products in high yields (up to 98%) and good enantioselectivities (up to 96%). In addition, these results were supported

  本文中，我们报道了作为均相和非均相有机催化剂的C 2对称磺酰胺的合成及其在羰基亲核体向β-硝基苯乙烯的对映选择性共轭1,4-Michael加成中的应用。有机催化剂在过渡状态下与β-硝基苯乙烯和烯胺形成氢键，模拟一种酶，最终产物的收率高（高达98％）和对映选择性（高达96％）。另外，这些结果得到密度泛函计算的支持。
• Enantioselective Aldol and Michael Additions of Achiral Enolates in the Presence of Chiral Lithium Amides and Amines
  作者：Eusebio Juaristi、Albert K. Beck、Jesper Hansen、Thomas Matt、Triptikumar Mukhopadhyay、Malgorzata Simson、Dieter Seebach

  DOI：10.1055/s-1993-26041

  日期：——

  It is now well established that lithium enolates and analogous derivatives generally exist as complex structures held together by noncovalent bonds ("supramolecules"). In particular, Li enolates aggregate to give dimers, tetramers, and higher oligomers, whose metal centers may be complexed by solvent molecules or chelating ligands. In addition, the anionoid part of the enolates may hydrogen-bond to weak acids such as secondary amines. Furthermore, such supramolecules can be product-forming species in synthetic reactions of Li enolates. This paper describes our observations of the temporary incorporation of chiral amines or chiral lithium amides into achiral lithium enolate aggregates (an interaction which is simply broken during aqueous workup!) to give enantiomerically enriched products. In particular, enantioselective aldol and Michael additions between achiral enolates and achiral aldehydes or achiral nitroolefins have been achieved in the presence of several chiral amines (or their lithium amides) derived from (S)-valine or (R,R)-tartaric acid. Finally, this report demonstrates the potential usefulness in asymmetric synthesis of ortho lithiation directed by chiral α-aminoalkoxides.

  目前已经充分确定，锂烯醇盐及其类似衍生物通常以非共价键结合而成的复杂结构（“超分子”）存在。特别是，锂烯醇盐聚集形成二聚体、四聚体和高阶寡聚体，其金属中心可能被溶剂分子或螯合配体络合。此外，烯醇盐的阴离子部分可能与二级胺等弱酸形成氢键。而且，这些超分子在锂烯醇盐的合成反应中可能是产物形成物种。本文描述了我们观察到的将手性胺或手性锂酰胺暂时掺入非手性锂烯醇盐聚集体（在水中处理时这种相互作用被简单破坏！）从而产生手性富集产物的现象。特别是，在几种由(S)-缬氨酸或(R,R)-酒石酸衍生的手性胺（或它们的锂酰胺）存在下，实现了非手性烯醇盐与非手性的醛或非手性硝基烯烃的立体选择性羟醛缩合反应和迈克尔加成反应。最后，本报告展示了手性α-氨基烷氧基导向的邻位锂化在对映选择性合成中的潜在应用价值。
• Functionalized proline with double hydrogen bonding potential: highly enantioselective Michael addition of carbonyl compounds to β-nitrostyrenes in brine
  作者：Satyajit Saha、Saona Seth、Jarugu Narasimha Moorthy

  DOI：10.1016/j.tetlet.2010.07.164

  日期：2010.10

  synthetic manipulation of S-proline allows access to prolinamides 5–7 as organocatalysts capable of double hydrogen bonding for enantioselective Michael addition reactions of carbonyl compounds to β-nitrostyrenes. It is shown that prolinamide catalyst 7 leads to addition products with a high diastereo- as well as enantioselectivity. The transition state structure involving the binding of electrophilic

  简单地合成S-脯氨酸即可获得脯氨酰胺5 – 7作为能够双氢键合的有机催化剂，用于羰基化合物与β-硝基苯乙烯的对映选择性迈克尔加成反应。结果表明，脯氨酰胺催化剂7导致具有高非对映选择性和对映选择性的加成产物。据信涉及通过两个H键结合亲电硝基苯乙烯的过渡态结构通过由甲苯磺酰基环介导的π，π堆积相互作用而进一步稳定。