(S)-2-((S)-2-nitro-1-(thiophen-2-yl)ethyl)cyclohexanone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (S)-2-((S)-2-nitro-1-(thiophen-2-yl)ethyl)cyclohexanone
• 英文别名: (S)-2-((S)-2-nitro-1-(thiophen-2-yl)ethyl)cyclohexan-1-one；2-(2-nitro-1-thiophen-2-yl-ethyl)cyclohexanone；(2S)-2-[(1S)-2-nitro-1-thiophen-2-ylethyl]cyclohexan-1-one
• 化学式: C₁₂H₁₅NO₃S
• 分子量: 253.322
• InChiKey: IXTLLOSYBIWABX-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  91.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (2R)-2-[tert-butyl(dimethyl)silyl]cyclohexan-1-one 在 氟化铵 、 氢氟酸 、 四丁基氟化铵 、 水 、 四氯化锡 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (S)-2-((S)-2-nitro-1-(thiophen-2-yl)ethyl)cyclohexanone
  参考文献：
  名称：

  α-Silyl Controlled Asymmetric Michael Additions of Acyclic and Cyclic Ketones to Nitroalkenes

  摘要：

  几乎对映纯的β-叔丁基二甲基硅基酮（R）-1和（S）-5被选择性地转化为相应的三甲基硅基烯醇醚（R）-2和（S，Z）-6。在SnCl4的存在下，对硝基烯烃进行后续的不对称迈克尔加成反应，可获得1,4-加合物3和7，且产率较高，立体异构体和对应异构体过剩。用n-Bu4NF、THF、NH4F/HF去除叔丁基二甲基硅基团，可获得α，β-二取代的γ-硝基酮（S，R）-4（de = 91-92%，ee >98%）和（R，S）-8（de >96%，ee >98%），总产率非常高。

  DOI：

  10.1055/s-1999-2715

文献信息

• Novel thiourea-amine bifunctional catalysts for asymmetric conjugate addition of ketones/aldehydes to nitroalkenes: rational structural combination for high catalytic efficiency
  作者：Jia-Rong Chen、Yi-Ju Cao、You-Quan Zou、Fen Tan、Liang Fu、Xiao-Yu Zhu、Wen-Jing Xiao

  DOI：10.1039/b925962g

  日期：——

  A series of thiourea-amine bifunctional catalysts have been developed by a rational combination of prolines with cinchona alkaloids, which are connected by a thiourea motif. The catalyst 3a, prepared from L-proline and cinchonidine, was found to be a highly efficient catalyst for the conjugate addition of ketones/aldehydes to a wide range of nitroalkenes (up to 98/2 dr and 96% ee). The privileged cinchonidine

  一系列 硫脲-胺双功能催化剂是通过脯氨酸与金鸡纳生物碱的合理组合而开发的，金鸡纳生物碱通过硫脲基序连接。催化剂3a由大号脯氨酸 和 辛可尼定被发现是一种高效的催化剂，用于将酮/醛共轭加成到各种各样的硝基烯烃中（高达98/2 dr和96％ee）。特权的辛可尼定骨架和硫脲基序对于反应活性和对映选择性是必不可少的。
• 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。
• 4-Trifluoromethanesulfonamidyl prolinol tert-butyldiphenylsilyl ether as a highly efficient bifunctional organocatalyst for Michael addition of ketones and aldehydes to nitroolefins
  作者：Chao Wang、Chun Yu、Changlu Liu、Yungui Peng

  DOI：10.1016/j.tetlet.2009.02.211

  日期：2009.5

  4-Trifluoromethanesulfonamidyl prolinol tert-butyldiphenylsilyl ether bifunctional organocatalyst 3a is a highly efficient catalyst for the asymmetric Michael addition reactions of ketones and aldehydes to nitrostyrenes, leading to syn-selective adducts with excellent yields (>99%), high diastereoselectivities (up to 99:1 dr) and excellent enantioselectivities (up to 99% ee). Control experiments suggested that the

  4-三氟甲烷磺酰胺基脯氨醇叔丁基二苯基甲硅烷基醚双官能团有机催化剂3a是酮和醛不对称迈克尔加成反应成硝基苯乙烯的高效催化剂，可生成具有良好收率（> 99％），高非对映选择性（高达99％）的顺式选择性加合物：1 dr）和出色的对映选择性（高达99％ee）。对照实验表明，在吡咯烷环的4位大基团（–CH 2 OTBDPS）与磺酰胺基之间的反式关系对于实现高收率和立体选择性很重要。
• Highly enantioselective Michael addition reactions in water catalyzed by an insoluble MPS-supported 4-sulfonamidyl prolinol tert-butyldiphenylsilyl ether
  作者：Yongming Chuan、Guihua Chen、Yungui Peng

  DOI：10.1016/j.tetlet.2009.04.011

  日期：2009.6

  The development of a highly efficient, insoluble, and non-swelling MPS-supported organocatalyst for the direct asymmetric Michael reaction of ketones and aldehydes to nitrostyrenes at room temperature in water is described. Excellent yields (up to 100%) and high stereoselectivities (up to 94% dr and 93% ee) were achieved with 10 mol % of the catalyst. The resin-bound catalyst was simply separated and

  描述了一种高效，不溶且不溶胀的MPS负载的有机催化剂的开发，该有机催化剂用于在室温下在水中将酮和醛直接进行不对称迈克尔反应，生成硝基苯乙烯。使用10摩尔％的催化剂可获得极佳的收率（最高100％）和高的立体选择性（最高94％dr和93％ee）。树脂结合的催化剂可以简单地通过过滤进行分离和回收，然后再用于六个连续的试验中，而活性和对映选择性均不会显着下降。
• [EN] ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS<br/>[FR] ORGANOCATALYSEURS ET PROCEDES D'UTILISATION DE CES DERNIERS DANS LA SYNTHESE CHIMIQUE
  申请人：STC UNM

  公开号：WO2006007586A1

  公开（公告）日：2006-01-19

  The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-­selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R', NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1­C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ('hydrocarbyl') group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R' are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R' are attached; and wherein said compound is free from a metal catalyst.

  本发明涉及一般包括有机催化剂的组合物，该催化剂促进立体选择性反应以及其合成和使用方法。特别地，本发明涉及无金属有机催化剂以促进立体选择性反应，以及其合成和使用方法。这些化合物具有以下结构的式（I）和（II）。其中X独立地选择自CH2、N-Ra、O、S或C=O；Y为 、N-Ra、O、S或C=O，但至少X或Y中的一个为 ，最好是X和Y都为 ；Ra为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6烷基，包括C3-C6环烷基，或可选择地取代的芳基，最好是可选择地取代的苯基；Rb为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6无环或C3-C6环烷基，CHO、N(Me)O、CO(S)Ra或式（III）的基团。其中Rc和Rd各自独立地为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C12烷基，更好地是C1-C6烷基，以及可选择地取代的芳基，或者Rc和Rd一起形成可选择地取代的碳环或可选择地取代的杂环；R1为OH、OR、NR'R'、NHC(=O)R、NHSO2R；R2为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，可选择地取代的芳基或=O基团（与=O连接的碳形成羰基基团）；R3为H、OH、F、C1、Br、I、Cl、可选择地取代的C1-C20烷基、烯基或炔基（'烃基'），最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，使得R3连接的碳具有R或S构型；R为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，R'和R'各自独立地为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基；或者R'和R'一起形成可选择地取代的杂环，最好是4到7成员的可选择地取代的杂环基团或与R'和R'连接的氮原子形成可选择地取代的杂芳基环；其中所述化合物不含金属催化剂。