(S)-1,3,4-trimethylcyclohex-3-ene-1-carbaldehyde

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (S)-1,3,4-trimethylcyclohex-3-ene-1-carbaldehyde
• 英文别名: (S)-1,3,4-trimethyl-cyclohex-3-enecarbaldehyde；(1S)-1,3,4-Trimethyl-3-cyclohexene-1-carbaldehyde；(1S)-1,3,4-trimethylcyclohex-3-ene-1-carbaldehyde
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: HPPUQZZCHCEJEW-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-1,3,4-trimethylcyclohex-3-ene-1-carbaldehyde 在 高氯酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 以1.29 g的产率得到1,3-endo-4-trimethylbicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  顺序狄尔斯-阿德耳反应/重排序列：官能化的双环[2.2.1]庚烷衍生物的合成及其相对构型的修订

  摘要：

  开发了一个顺序的Diels-Alder反应/重排序列，用于合成各种功能化的双环[2.2.1]庚烷，作为新型花香和木质香气。重排的结果取决于二烯的取代模式。二维NMR分析确定了最初错配的双环[2.2.1]庚酮的正确相对构型。此外，当通过手性路易斯酸催化起始的DA反应时，可以以高达96.5：3.5的对映体比例（er）获得包括（+）-丁香酮在内的双环[2.2.1]庚烷衍生物。

  DOI：

  10.1021/jo500942a
• 作为产物：
  描述：

  2-甲基丙烯醛 、 2,3-二甲基-1,3-丁二烯 在 四氯化锡 、 (S)-2-(O-甲基)苯-CBS-恶唑硼烷 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (S)-1,3,4-trimethylcyclohex-3-ene-1-carbaldehyde
  参考文献：
  名称：

  顺序狄尔斯-阿德耳反应/重排序列：官能化的双环[2.2.1]庚烷衍生物的合成及其相对构型的修订

  摘要：

  开发了一个顺序的Diels-Alder反应/重排序列，用于合成各种功能化的双环[2.2.1]庚烷，作为新型花香和木质香气。重排的结果取决于二烯的取代模式。二维NMR分析确定了最初错配的双环[2.2.1]庚酮的正确相对构型。此外，当通过手性路易斯酸催化起始的DA反应时，可以以高达96.5：3.5的对映体比例（er）获得包括（+）-丁香酮在内的双环[2.2.1]庚烷衍生物。

  DOI：

  10.1021/jo500942a

文献信息

• Chiral Anion Directed Asymmetric Carbocation-Catalyzed Diels-Alder Reactions
  作者：Shengjun Ni、Veluru Ramesh Naidu、Johan Franzén

  DOI：10.1002/ejoc.201501621

  日期：2016.3

  carbocation has re-emerged as a highly efficient Lewis acid catalyst for a variety of organic transformations. However, the goal of asymmetric carbocation catalysis has so far been out of reach mainly as a result of difficulties associated with the preparation of stable chiral carbocations. Here, we describe developments towards asymmetric carbocation catalysis based on the concept of chiral-anion-directed

  近年来，碳正离子重新成为各种有机转化的高效路易斯酸催化剂。然而，迄今为止，不对称碳正离子催化的目标仍然遥不可及，主要是由于与制备稳定的手性碳正离子相关的困难。在这里，我们描述了基于手性阴离子导向催化概念的不对称碳阳离子催化的发展。手性三苯甲基鎓盐可以通过将三苯甲基氯衍生物与手性膦酸盐、磷酰胺、双（磺酰基）酰胺和双（硫酰基）酰胺银盐或钠盐混合而方便地原位制备。结果表明，双（硫基）酰胺/三苯甲基鎓离子盐以高达 53% 的对映体过量催化 Diels-Alder 反应。
• Bi-functional complexes and methods for making and using such complexes
  申请人：Gouliaev Alex Haahr

  公开号：US11225655B2

  公开（公告）日：2022-01-18

  The present invention is directed to a method for the synthesis of a bi-functional complex comprising a molecule part and an identifier oligonucleotide part identifying the molecule part. A part of the synthesis method according to the present invention is preferably conducted in one or more organic solvents when a nascent bi-functional complex comprising an optionally protected tag or oligonucleotide identifier is linked to a solid support, and another part of the synthesis method is preferably conducted under conditions suitable for enzymatic addition of an oligonucleotide tag to a nascent bi-functional complex in solution.

  本发明涉及一种合成双功能复合物的方法，该复合物包括分子部分和识别分子部分的识别寡核苷酸部分。根据本发明的合成方法的一部分优选在一种或多种有机溶剂中进行，此时包含可选保护标签或寡核苷酸标识符的新生双功能复合物与固体支持物相连接，合成方法的另一部分优选在适合于将寡核苷酸标签酶加到溶液中的新生双功能复合物的条件下进行。
• Enantioselective catalysts based on the chiral fragment (η5-C5Me5)Ir(Prophos) for Diels–Alder reactions
  作者：Daniel Carmona、Fernando Viguri、Ainara Asenjo、Fernando J. Lahoz、Pilar García-Orduña、Luis A. Oro

  DOI：10.1016/j.molcata.2014.01.021

  日期：2014.4

  The aqua complex (S-Ir,R-C)-[(eta(5)-C5Me5)Ir(Prophos)(H2O)][SbF6](2) [Prophos = (R)-propane-1,2-diyl-bis(diphenylphosphane)] is an active precursor for the asymmetric Diels-Alder reaction of acyclic enals with cyclopentadiene, 2,3-dimethylbutadiene and isoprene. Enantioselectivities up to 78% ee are achieved. The intermediate Lewis acid-dienophile complex (S-Ir,R-C)-[(eta(5)-C5Me5)Ir(Prophos)(ethyl acrolein)][SbF6](2) has been isolated and completely characterized, including the X-ray crystal structure determination. Structural parameters indicate that the disposition of the coordinated dienophile is controlled by CH/pi attractive interactions established between a phenyl group of the Prophos ligand and the aldehyde proton of the coordinated enal. Proton NMR data indicate that these interactions are maintained in solution. From diffractometric and spectroscopic data, the origin of the enantioselectivity is discussed. (C) 2014 Elsevier B.V. All rights reserved.
• Catalytic Enantioselective Diels−Alder Reaction via a Chiral Indium(III) Complex
  作者：Yong-Chua Teo、Teck-Peng Loh

  DOI：10.1021/ol050518d

  日期：2005.6.1

  A chiral indium complex has been developed to effect high enantioselectivities in catalyzing enantioselective Diels-Alder reaction. The cycloaddition of a variety of cyclic and open-chained dienes to 2-methacrolein and 2-bromoacrolein resulted in good yields and excellent enantioselectivities (up to 98% ee).
• Catalytic Enantioselective Diels−Alder Reaction in Ionic Liquid via a Recyclable Chiral In(III) Complex
  作者：Fan Fu、Yong-Chua Teo、Teck-Peng Loh

  DOI：10.1021/ol062481i

  日期：2006.12.1

  A recyclable, air-and moisture- stable chiral indium complex in [hmim][ PF6-] ionic liquid has been developed. The cycloaddition of a variety of cyclic and open- chained dienes to 2-methacrolein and 2- bromoacrolein resulted in good yields and excellent enantioselectivities ( up to 98% ee). Moreover, the chiral In( III) complex can be reused for seven successive cycles with comparable enantioselectivities and yields without loss of catalytic activity.