(R)-1-(2-nitro-1-phenylethyl)cyclopentanecarbaldehyde

• 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: (R)-1-(2-nitro-1-phenylethyl)cyclopentanecarbaldehyde
• 英文别名: 1-((R)-2-nitro-1-phenylethyl)cyclopentanecarbaldehyde；1-[(1R)-2-nitro-1-phenylethyl]cyclopentane-1-carbaldehyde
• 化学式: C₁₄H₁₇NO₃
• 分子量: 247.294
• InChiKey: QMCAAXWWBJWWGE-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  4
• 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

• 作为反应物：
  描述：

  (R)-1-(2-nitro-1-phenylethyl)cyclopentanecarbaldehyde 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以60%的产率得到4-phenyl-2-azaspiro[4.4]non-1-ene 2-oxide
  参考文献：
  名称：

  吡咯烷-樟脑衍生物作为α，α-二取代醛向β-硝基烯烃的不对称迈克尔加成反应的有机催化剂：无溶剂条件下含碳季铵的构建

  摘要：

  Abstractmagnified imageA novel pyrrolidine‐camphor organocatalyst 3 was designed, synthesized and proven to be an efficient catalyst for the asymmetric Michael reaction. Treatment of α,α‐disubstituted aldehydes with β‐nitroalkenes in the presence of 20 mol% organocatalyst 3 and 20 mol% benzoic acid under solvent‐free conditions provided the desired Michael product possessing an all‐carbon quaternary center with high chemical yields (up to 99% yield) and high levels of enantioselectivities (up to 95% ee).

  DOI：

  10.1002/adsc.200800771
• 作为产物：
  描述：

  环戊基甲醛 、 β-硝基苯乙烯 在 (S)-2-(pyrrolidin-2-ylmethoxy)isoindoline-1,3-dione 、 对硝基苯甲酸 作用下， 以 neat (no solvent) 为溶剂， 反应 48.33h， 以87%的产率得到(R)-1-(2-nitro-1-phenylethyl)cyclopentanecarbaldehyde
  参考文献：
  名称：

  吡咯烷-氧酰亚胺催化的α，α-二取代醛向硝基烯烃的不对称迈克尔加成

  摘要：

  报道了使用吡咯烷-氧酰亚胺催化剂将α，α-二取代醛有机催化对映选择性迈克尔加成到硝基烯烃上。该反应在纯净条件下在0°C下以15 mol％的催化剂和10 mol％的对硝基苯甲酸为添加剂可有效地进行；这导致形成具有全碳四元中心并具有良好收率和对映选择性的迈克尔加合物。

  DOI：

  10.1016/j.tetasy.2015.07.009

文献信息

• [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CH2、N-Ra、O、S或C=O，但至少X或Y中的一个为CH2，最好是X和Y都为CH2；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。
• ORGANOCATALYST
  申请人：Chen Kwunmin

  公开号：US20110040104A1

  公开（公告）日：2011-02-17

  The present invention provides an organocatalyst of formula (I), wherein R 1 is —H, —OH, —O—Si(R 4 )(R 5 )(R 6 ) or C 1-6 alkoxy, in which R 4 , R 5 and R 6 are identical or different and independently selected from the group consisting of C 1-6 alkyl, phenyl and phenyl substituted with C 1-6 alkyl; R 2 is —OH or ═O; X 1 is one selected from the group consisting of —NH—, —S— and X 2 is one selected from the group consisting of —C(═O)—, —CH 2 — and and X 1 is different from X 2 . The high yield and enantioselectivity of an addition reaction are obtained by using the organocatalyst of the present invention.

  本发明提供了一种式(I)的有机催化剂，其中R1为—H，—OH，—O—Si(R4)(R5)(R6)或C1-6烷氧基，其中R4、R5和R6相同或不同，并且独立地选自由C1-6烷基、苯基和苯基上取代的C1-6烷基的群；R2为—OH或═O；X1为从—NH—、—S—中选择的一种；X2为从—C(═O)—、—CH2—中选择的一种；X1与X2不同。通过使用本发明的有机催化剂，可以获得加成反应的高产率和对映选择性。
• Enantio- and Diastereoselective Michael Addition Reactions of Unmodified Aldehydes and Ketones with Nitroolefins Catalyzed by a Pyrrolidine Sulfonamide
  作者：Jian Wang、Hao Li、Bihshow Lou、Liansuo Zu、Hua Guo、Wei Wang

  DOI：10.1002/chem.200600115

  日期：2006.5.24

  Chiral (S)-pyrrolidine trifluoromethanesulfonamide has been shown to serve as an effective catalyst for direct Michael addition reactions of aldehydes and ketones with nitroolefins. A wide range of aldehydes and ketones as Michael donors and nitroolefins as acceptors participate in the process, which proceeds with high levels of enantioselectivity (up to 99 % ee) and diastereoselectivity (up to 50:1

  已显示手性（S）-吡咯烷三氟甲磺酰胺可作为醛和酮与硝基烯烃的直接迈克尔加成反应的有效催化剂。作为迈克尔供体的多种醛和酮以及作为受体的硝基烯烃参与了该过程，该过程以高水平的对映选择性（高达99％ee）和非对映选择性（高达50：1 dr）进行。该方法已成功地用于有效的H（3）激动剂Sch 50917的有效合成中。此外，已经开发了一种用于制备（S）-吡咯烷三氟甲烷磺酰胺的实用三步程序。已经通过使用从头算和密度泛函方法研究了由该吡咯烷磺酰胺催化的参与迈克尔加成反应的高水平立体化学控制。已计算出了限速C-C键形成步骤的过渡态结构，该结构对应于关键烯胺中间体的反应构象的表面和表面加成。对这些结构的分析表明，氢键在催化中起重要作用，并且醛在形成2R，3S产物的反应中si-face攻击的能垒比导致2S，3R产物的表面攻击要低。 。相反，在酮的反应中，用于表面添加的能垒比用于硅表面添加的能垒低。在这些迈克尔
• Readily Accessible 9-epi-amino Cinchona Alkaloid Derivatives Promote Efficient, Highly Enantioselective Additions of Aldehydes and Ketones to Nitroolefins
  作者：Séamus H. McCooey、Stephen J. Connon

  DOI：10.1021/ol0628006

  日期：2007.2.1

  from commercially available starting materials, have been shown to promote highly enantio- and diastereoselective Michael-type addition reactions between enolizable carbonyl compounds and nitroalkenes of broad scope. The influence of both the absolute and relative stereochemistry at C-9 on catalyst performance has also been assessed. [reaction: see text].

  通过一锅法可从市售原料中获得的简单金鸡纳生物碱衍生物已显示出可促进可烯丙基的羰基化合物与广泛范围的硝基烯烃之间的高度对映和非对映选择性迈克尔型加成反应。还评估了C-9处绝对和相对立体化学对催化剂性能的影响。[反应：请参见文字]。
• Highly enantioselective conjugate addition of aldehydes to nitroolefins catalyzed by chiral bifunctional sulfamides
  作者：Xue-jing Zhang、Sheng-ping Liu、Xue-ming Li、Ming Yan、Albert S. C. Chan

  DOI：10.1039/b818582d

  日期：——

  Chiral bifunctional sulfamides were found to be highly efficient organocatalysts for the conjugate addition of aldehydes to nitroolefins in the presence of base additives.

  手性双功能磺酰胺被发现是醛与亚硝烯在碱性添加剂存在下进行 conjugate 加成反应的高效有机催化剂。