ethyl (6R)-3,4-dimethyl-6-methylsulfanyl-2,5-dihydrothiopyran-6-carboxylate

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: ethyl (6R)-3,4-dimethyl-6-methylsulfanyl-2,5-dihydrothiopyran-6-carboxylate
• 化学式: C₁₁H₁₈O₂S₂
• 分子量: 246.395
• InChiKey: GTAXFMQTSFRSCB-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  Ethyl 3,6-dihydro-4,5-dimethyl-2-methylthio-2H-thiopyran-2-carboxylate 生成 ethyl (6R)-3,4-dimethyl-6-methylsulfanyl-2,5-dihydrothiopyran-6-carboxylate 、 ethyl (6S)-3,4-dimethyl-6-methylsulfanyl-2,5-dihydrothiopyran-6-carboxylate
  参考文献：
  名称：

  Asymmetric diastereoselective thia-hetero-Diels–Alder reactions of dithioesters

  摘要：

  Asymmetric thia-Diels-Alder reactions involving new dithioesters bearing a chiral auxiliary are described, with diastereoselectivities up to 78%. Double-stereodifferentiating experiments employing chiral substrates in the presence of a chiral Lewis acid catalyst have been also carried out and, in this case, a diastereomeric excess of 90% was reached. The absolute stereochemistry of cycloadducts resulting from dithiooxalates and carbonyloxazolidinone dithioesters was assigned based on an X-ray structure and chemical correlation. In order to rationalize the sense of the chiral induction, stereochemical models for Cu(II)/bis(oxazoline)/dithioester complexes are proposed. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.039

文献信息

• Recent Developments in Asymmetric Hetero-Diels-Alder Reactions of Dithioesters
  作者：Hélène Dentel、Mihaela Gulea

  DOI：10.1080/10426507.2012.729113

  日期：2013.4.1

  Abstract Recent studies dealing with asymmetric thia-Diels-Alder reactions of dithioesters as heterodienophiles are described. A diastereoselective version involving new chiral dithioesters and the first example of a catalytic enantioselective version are described. The absolute stereochemistry of the cycloadducts was assigned based on an X-ray structure and chemical correlation. In order to rationalize

  摘要描述了最近关于作为亲异二烯体的二硫酯的不对称硫杂-狄尔斯-阿尔德反应的研究。描述了涉及新手性二硫酯的非对映选择性版本和催化对映选择性版本的第一个例子。环加合物的绝对立体化学是根据 X 射线结构和化学相关性确定的。为了使实验观察到的手性诱导合理化，提出了 Cu(II)/BOX/二硫酯配合物的立体化学模型。图形概要
• First catalytic enantioselective version of a thia hetero-Diels–Alder reaction with dithioesters
  作者：Hélène Dentel、Isabelle Chataigner、Fabien Le Cavelier、Mihaela Gulea

  DOI：10.1016/j.tetlet.2010.09.055

  日期：2010.11

  The first example of a catalytic asymmetric thia hetero-Diels-Alder reaction, in which a chiral Lewis acid activates the thiocarbonyl dienophile, is described. The reactions catalyzed by copper(II)-bis(oxazolines) complexes of three dithioesters with simple dienes (such as cyclopentadiene or 2,3-dimethy1-1,3-butadiene) afford optically active dihydrothiopyrans with ees up to 82%. Some aspects of the reaction were investigated by computational means. (C) 2010 Elsevier Ltd. All rights reserved.
• Asymmetric diastereoselective thia-hetero-Diels–Alder reactions of dithioesters
  作者：Hélène Dentel、Isabelle Chataigner、Jean-François Lohier、Mihaela Gulea

  DOI：10.1016/j.tet.2012.01.039

  日期：2012.3

  Asymmetric thia-Diels-Alder reactions involving new dithioesters bearing a chiral auxiliary are described, with diastereoselectivities up to 78%. Double-stereodifferentiating experiments employing chiral substrates in the presence of a chiral Lewis acid catalyst have been also carried out and, in this case, a diastereomeric excess of 90% was reached. The absolute stereochemistry of cycloadducts resulting from dithiooxalates and carbonyloxazolidinone dithioesters was assigned based on an X-ray structure and chemical correlation. In order to rationalize the sense of the chiral induction, stereochemical models for Cu(II)/bis(oxazoline)/dithioester complexes are proposed. (C) 2012 Elsevier Ltd. All rights reserved.