(R )-5-oxo-3,5-diphenylpentanal | 166114-67-6

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (R )-5-oxo-3,5-diphenylpentanal
• 英文别名: (R)-5-oxo-3,5-diphenyl-pentanal；(R)-5-oxo-3,5-diphenylpentanal；5-oxo-3,5-diphenylpentanal；(3R)-5-oxo-3,5-diphenylpentanal
• CAS: 166114-67-6
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: GKZOTTIKNGAVFQ-MRXNPFEDSA-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：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R )-5-oxo-3,5-diphenylpentanal 在 sodium chlorite 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 作用下， 以 水 、 叔丁醇 为溶剂， 反应 8.5h， 以50%的产率得到(S)-3,5-Diphenyl-5-oxopentanoic acid
  参考文献：
  名称：

  在对映选择性催化形式的氮杂[3 + 3]环加成反应中，以二苯丙醇基甲硅烷基醚为催化剂，以形成对映体富集的哌啶。

  摘要：

  DOI：

  10.1002/anie.200800662
• 作为产物：
  描述：

  (Z,3S)-5-[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl]oxy-1,3-diphenylpent-4-en-1-one 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到(R )-5-oxo-3,5-diphenylpentanal
  参考文献：
  名称：

  Barluenga, Jose; Montserrat, Javier M.; Florez, Josefa, Angewandte Chemie, 1994, vol. 106, # 13, p. 1451 - 1454

  摘要：

  DOI：

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。
• ORGANIC SALTS AND METHOD FOR PRODUCING CHIRAL ORGANIC COMPOUNDS
  申请人：List Benjamin

  公开号：US20090030216A1

  公开（公告）日：2009-01-29

  The invention relates to a method for producing chiral organic compounds by asymmetric catalysis, using ionic catalysts comprising a chiral catalyst anion. The claimed method is suitable for reactions which are carried out over cationic intermediate stages, such as iminium ions or acyl pyridinium ions. The invention enables the production of chiral compounds with high ee values, that until now could only be obtained by means of costly purification methods.

  该发明涉及一种通过不对称催化制备手性有机化合物的方法，使用包括手性催化剂阴离子的离子催化剂。所述方法适用于在阳离子中间体阶段进行的反应，例如亚胺离子或酰基吡啶离子。该发明实现了具有高ee值的手性化合物的生产，直到现在只能通过昂贵的纯化方法获得。
• Asymmetric Direct Michael Addition of Acetophenone to α,β-Unsaturated Aldehydes
  作者：Jinxing Ye、Wenjun Li、Wenbin Wu、Juanjuan Yang、Xinmiao Liang

  DOI：10.1055/s-0030-1258459

  日期：2011.4

  The asymmetric direct Michael addition of α,β-unsaturated aldehydes with acetophenone catalyzed by a Jørgensen-Hayashi­ catalyst in methanol was developed and the corresponding Michael products of δ-keto aldehydes could be afforded in up to 82% yield and 98% ee. asymmetric catalysis - Michael additions - ketones - aldehydes - enals

  研究了Jørgensen-Hayashi催化剂在甲醇中催化的苯乙酮与α，β-不饱和醛的不对称直接迈克尔加成反应，δ-酮醛的相应迈克尔产物收率可达82％，ee为98％。 不对称催化-迈克尔加成-酮-醛-烯醛
• Nucleophilicity Parameters of Enamides and Their Implications for Organocatalytic Transformations
  作者：Biplab Maji、Sami Lakhdar、Herbert Mayr

  DOI：10.1002/chem.201103519

  日期：2012.4.27

  The kinetics of the reactions of eleven substituted enamides with benzhydrylium ions (diarylcarbenium ions) were determined in acetonitrile solution. The second‐order rate constants follow the correlation log k2(20 °C)=sN(E+N), which allowed us to derive reactivity parameters N and sN. With 4.6

  在乙腈溶液中测定了11个取代的酰胺与苯甲酰鎓离子（二芳基碳鎓离子）的反应动力学。二阶速率常数遵循相关日志 ķ 2（20℃）=小号Ñ（Ë + Ñ），这使我们能够派生反应参数Ñ和š Ñ。当4.6 < N <7.1时，酰胺的亲核性与烯醇醚，未活化或弱活化的吲哚和吡咯类似。所述的组合Ñ和š Ñ参数与先前报道È典型的迈克尔受体，α，β-不饱和亚胺离子和氯化剂六氯环己-2,4-二烯酮的参数使我们能够可靠地重现与这些亲电子试剂反应的实验速率常数。酰胺与α，β-不饱和亚胺离子的反应仅在存在碱（例如2,6-二甲基吡啶）的情况下进行，这可以通过亚胺离子的路易斯酸度低来解释。讨论了这些结果对在有机催化反应中使用酰胺的影响。
• Enantioselective Organocatalytic Mukaiyama−Michael Addition of Silyl Enol Ethers to α,β-Unsaturated Aldehydes
  作者：Wei Wang、Hao Li、Jian Wang

  DOI：10.1021/ol0503337

  日期：2005.4.14

  enantioselective, organocatalytic Mukaiyama-Michael addition reaction of silyl ethers and alpha,beta-unsaturated aldehydes has been developed. The process, catalyzed by MacMillan's chiral imidazolidinone, affords delta-keto aldehydes in high yields (56-87%) and high enantioselectivities (85-97% ee). Moreover, the reaction is applicable to a wide range of silyl ethers and alpha,beta-unsaturated aldehydes and, as such

  [反应：见正文]已开发出甲硅烷基醚与α，β-不饱和醛的高度对映选择性的有机催化Mukaiyama-Michael加成反应。由麦克米伦的手性咪唑啉酮催化的这一方法可提供高产率（56-87％）和高对映选择性（85-97％ee）的δ-酮醛。而且，该反应适用于多种甲硅烷基醚和α，β-不饱和醛，因此，提供了进入一系列重要的合成构件的途径。