(R)-(+)-2-(p-tert-Butylphenyl)methyl-2-methyl-4-pentenal | 135055-78-6

• 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: (R)-(+)-2-(p-tert-Butylphenyl)methyl-2-methyl-4-pentenal
• 英文别名: (R)-(+)-2-<(4-tert-Butylphenyl)methyl>-2-methyl-2-pentenal；(R)-2-(4-(tert-butyl)benzyl)-2-methylpent-4-enal；(2R)-2-[(4-tert-butylphenyl)methyl]-2-methylpent-4-enal
• CAS: 135055-78-6
• 化学式: C₁₇H₂₄O
• 分子量: 244.377
• InChiKey: VTXWTJSHQNFMKC-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (S)-1-[(E)-3-(4-tert-Butyl-phenyl)-2-methyl-propenyl]-pyrrolidine-2-carboxylic acid allyl ester 在 四(三苯基膦)钯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 45.0h， 生成 (R)-(+)-2-(p-tert-Butylphenyl)methyl-2-methyl-4-pentenal 、 (S)-2-<(4-tert-Butylphenyl)methyl>-2-methyl-2-pentenal
  参考文献：
  名称：

  Asymmetric induction reactions. V. The palladium-catalyzed asymmetric .alpha.-allylation of carbonyl compounds with chiral allyl esters via enamines and imines

  摘要：

  A novel and excellent method for asymmetric alpha-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl eaters has been developed. Readily available chiral allyl eaters having chirality at the alpha-position of the eater carbonyl group, such as (S)-proline and other (S)-alpha-amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding alpha-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.

  DOI：

  10.1021/jo00080a033

文献信息

• Asymmetric induction reactions. IV. Palladium-catalyzed asymmetric allylations of chiral enamines bearing phosphine groups.
  作者：Kunio HIROI、Jun ABE

  DOI：10.1248/cpb.39.616

  日期：——

  The palladium-catalyzed asymmetric allylations of chiral enamines, derived from (S)-2-(diphenylphosphinomethyl)pyrrolidine, produced optically active α-allyl carbonyl compounds in high optical yields. The phosphino group in the chiral enamines presumably serves as a chiral ligand in these palladium-catalyzed reactions. In the transition states of π-allylpalladium complexes coordinated with the intramolecular phosphine group, the anionic counterparts or allylating reagents are considered to play an important role in controlling of the grade of the enantioselectivity.

  钯催化的手性烯胺的不对称烯基化反应，源自(S)-2-(二苯膦甲基)吡咯烷，产生了光学活性α-烯基羰基化合物，并且光学产率很高。手性烯胺中的磷基团在这些钯催化反应中很可能作为手性配体。在与分子内磷烷基团配位的π-烯基钯配合物的过渡态中，阴离子对应物或烯基化试剂被认为在控制对映选择性的等级方面起着重要作用。
• Counterion-Enhanced Pd/Enamine Catalysis: Direct Asymmetric α-Allylation of Aldehydes with Allylic Alcohols by Chiral Amines and Achiral or Racemic Phosphoric Acids
  作者：Ádám Márk Pálvölgyi、Jakob Smith、Michael Schnürch、Katharina Bica-Schröder

  DOI：10.1021/acs.joc.0c02385

  日期：2021.1.1

  catalytic procedure for the direct asymmetric α-allylation of branched aldehydes. The use of simple chiral amines and easily prepared achiral or racemic phosphoric acids, together with a suitable Pd-source resulted in a highly active and enantioselective catalyst system for the allylation of various α-branched aldehydes with different allylic alcohols. The reported procedure could provide an easy access to

  我们报告了一种直接有效的 Pd/烯胺催化方法，用于支化醛的直接不对称 α-烯丙基化。使用简单的手性胺和容易制备的非手性或外消旋磷酸，再加上合适的 Pd 源，产生了一种高活性和对映选择性的催化剂体系，用于各种 α-支化醛与不同烯丙醇的烯丙基化。报告的程序可以提供对两种产品对映体的轻松访问。此外，对富含对映体的醛进行了两种可能的正交衍生化，而对映选择性没有任何降低。