(S)-2-allyl-2-((1,3-dioxoisoindolin-2-yl)methyl)cyclopentanone | 1362388-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (S)-2-allyl-2-((1,3-dioxoisoindolin-2-yl)methyl)cyclopentanone
• 英文别名: 2-((1-allyl-2-oxocyclopentyl)methyl)isoindoline-1,3-dione；2-[[(1S)-2-oxo-1-prop-2-enylcyclopentyl]methyl]isoindole-1,3-dione
• CAS: 1362388-05-3
• 化学式: C₁₇H₁₇NO₃
• 分子量: 283.327
• InChiKey: UHCXIAHWNHWJFC-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  54.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  allyl 1-((1,3-dioxoisoindolin-2-yl)methyl)-2-oxocyclopentanecarboxylate 在 (S)-(CF₃)₃-t-BuPHOX 、 tris-(dibenzylideneacetone)dipalladium(0) 作用下， 以 甲苯 为溶剂， 反应 23.0h， 以92%的产率得到(S)-2-allyl-2-((1,3-dioxoisoindolin-2-yl)methyl)cyclopentanone
  参考文献：
  名称：

  Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones

  摘要：

  The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF3)(3)-t-BuPHOX ligand, alpha-quaternary cyclopentanones were isolated in yields up to >99% with ee's up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.

  DOI：

  10.1021/acs.orglett.5b02376

文献信息

• Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies
  作者：Douglas C. Behenna、Justin T. Mohr、Nathaniel H. Sherden、Smaranda C. Marinescu、Andrew M. Harned、Kousuke Tani、Masaki Seto、Sandy Ma、Zoltán Novák、Michael R. Krout、Ryan M. McFadden、Jennifer L. Roizen、John A. Enquist、David E. White、Samantha R. Levine、Krastina V. Petrova、Akihiko Iwashita、Scott C. Virgil、Brian M. Stoltz

  DOI：10.1002/chem.201003383

  日期：2011.12.9

  functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target‐directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner‐sphere mechanism involving binding of the prochiral

  在钯配合物与各种膦恶唑啉 (PHOX) 配体的存在下，通过不稳定的前手性烯醇化亲核试剂对烯丙基和炔丙基亲电子试剂进行新颖的对映选择性烷基化来获得 α-季酮。三类烯醇化物前体获得了优异的产率和高对映体过量：烯醇碳酸酯、烯醇硅烷和外消旋 β-酮酯。这些底物类别中的每一种在产率和对映选择性方面都具有几乎相同的效率。报道了催化剂的发现和开发、反应条件的优化、反应范围的探索以及在靶向合成中的应用。实验观察表明，这些烷基化反应通过一种不寻常的内球机制发生，涉及前手性烯醇化亲核试剂直接与钯中心结合。