Ethyl 3,6-dihydro-4,5-dimethyl-2-methylthio-2H-thiopyran-2-carboxylate | 73496-46-5

• 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 3,6-dihydro-4,5-dimethyl-2-methylthio-2H-thiopyran-2-carboxylate
• 英文别名: Ethyl 3,4-dimethyl-6-methylsulfanyl-2,5-dihydrothiopyran-6-carboxylate
• CAS: 73496-46-5
• 化学式: C₁₁H₁₈O₂S₂
• 分子量: 246.395
• InChiKey: GTAXFMQTSFRSCB-UHFFFAOYSA-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

• 作为反应物：
  描述：

  Ethyl 3,6-dihydro-4,5-dimethyl-2-methylthio-2H-thiopyran-2-carboxylate 在 potassium hydroxide 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 15.0h， 生成 4,5-dimethyl-2-(methylsulfanyl)-3,6-dihydro-2H-thiopyran-2-carboxylic acid brucinium salt
  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
• 作为产物：
  描述：

  1,3-二硫烷-2-甲酸乙酯 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 32.0h， 生成 Ethyl 3,6-dihydro-4,5-dimethyl-2-methylthio-2H-thiopyran-2-carboxylate
  参考文献：
  名称：

  Generation of .alpha.-oxo dithioesters by dithiolanium ylide cycloreversion. Synthesis of 2-acyl-3,6-dihydro-2H-thiopyrans

  摘要：

  DOI：

  10.1021/jo01301a012

文献信息

• Cyclopentene Synthesis from 1,3-Dienes via Base-Induced Ring Contraction of 3,6-Dihydro-2<i>H</i>-thiopyrans:  Studies on Diastereoselection and Mechanism
  作者：Scott D. Larsen、Peter V. Fisher、Brian E. Libby、Randy M. Jensen、Stephen A. Mizsak、William Watt、Warren R. Ronk、Scott T. Hill

  DOI：10.1021/jo960537o

  日期：1996.1.1

  component. In some cases, reducing the temperature during the ring contraction resulted in the isolation of good yields of vinyl cyclopropanes of high isomeric purity. With one substrate, highly diastereoselective rearrangement of a vinyl cyclopropane to a cyclopentene was unambiguously demonstrated, suggesting that this might be a key feature of the overall ring contraction mechanism.

  描述了对由3，6-二氢-2H-硫代吡喃新合成环戊烯的范围和机理的研究。使在α位置被吸电子基团取代的卤代烷与硫代硫酸钠反应，生成相应的Bunte盐，通过用温和的碱处理消除亚硫酸氢盐的元素，可以将其转化为反应性硫代羰基化合物。通过1，3-二烯原位捕获可提供良好的收率，其中各种3，6-二氢-2H-硫代吡喃在2-位被吸电子基团取代。这些环加合物在低温下暴露于强碱下会引起新的环收缩，在用甲基碘淬灭后得到2-（甲硫基）-3-环戊烯。发现在这些环戊烯的产生过程中表现出的非对映选择性水平取决于二氢噻喃的2-位上的吸电子基团的性质以及二烯组分中最初存在的取代模式。在某些情况下，在环收缩期间降低温度导致分离出高产率的高异构体纯度的乙烯基环丙烷。在一个底物上，乙烯基环丙烷向环戊烯的高度非对映选择性重排得到了明确证明，表明这可能是整个环收缩机制的关键特征。在环收缩过程中降低温度导致分离出高产率的高异构体纯度的乙烯
• 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
• 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.
• Generation of .alpha.-oxo dithioesters by dithiolanium ylide cycloreversion. Synthesis of 2-acyl-3,6-dihydro-2H-thiopyrans
  作者：E. Vedejs、M. J. Arnost、J. M. Dolphin、J. Eustache

  DOI：10.1021/jo01301a012

  日期：1980.6