cis-2,3-Diethylthiirane | 30465-45-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环丙烷
• 英文名称: cis-2,3-Diethylthiirane
• 英文别名: cis-2,3-Diethylepisulfid；cis-Diethylthiiran；(2R,3S)-2,3-diethylthiirane
• CAS: 30465-45-3
• 化学式: C₆H₁₂S
• 分子量: 116.227
• InChiKey: BIQQKNMQSYWGFU-OLQVQODUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-2,3-Diethylthiirane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以59%的产率得到anti,cis-1,2-diethylthiirane S-oxide
  参考文献：
  名称：

  Theoretical and Experimental Analyses of the Deprotonation of Thiirane S-Oxides: The Stereoselective Formation of trans-Alkyl- and gem-Silylethenesulfenate Anions

  摘要：

  Experimental and theoretical studies of the regioselective deprotonation of thiirane S-oxides are reported. Experimentally under the reaction conditions of LiHMDS/THF/-78 degrees C with anti-alkylthiirane S-oxides or anti-silylthiirane S-oxides as starting materials, the products of ring-opening are (E)-2-alkylethenesulfenate and 1-silylethenesulfenate anions, respectively. Experiments involving deuterium labeling clearly indicate that a regioselective deprotonation reaction was followed by a stereoselective ring-opening. Ab initio methods at both the Hartree-Fock and Moller-Plesset perturbation theory levels with the 6-31+G(d) basis set were used to examine both lithiated methyl- and silylthiirane S-oxides. Of the possible anti-substituted species, the coordination of the lithium anti to the methyl and gem to the silyl is predicted to be the most stable. These stable intermediates with the lithium syn to the sulfoxide could ring-open to yield the experimentally observed products.

  DOI：

  10.1021/ja00106a022
• 作为产物：
  描述：

  3-己酮 在 sodium tetrahydroborate 作用下， 以 二氯甲烷 、 异丙醇 为溶剂， 反应 1.5h， 生成 cis-2,3-Diethylthiirane
  参考文献：
  名称：

  烯烃立体选择性合成的新策略

  摘要：

  描述了经由中间体S-（β-氧代烷基）硫代磷酸酯及其硒代类似物将酮高度立体选择性地转化为（Z）-烯烃。

  DOI：

  10.1016/s0040-4039(00)92177-4

文献信息

• An Expeditious One-Pot Synthesis of Thiiranes from α-Halo Ketones in Solvent­-Free Conditions Using Microwaves
  作者：Lal Dhar Yadav、Ritu Kapoor

  DOI：10.1055/s-2002-35222

  日期：——

  Thiiranes are obtained in excellent yields and with high diastereoselectivity upon microwave irradiation of a mixture of α-haloketones, O,O-diethyl hydrogen phosphorodithioate and alumina-supported sodium borohydride in solvent-free conditions.

  在无溶剂条件下，将α-卤代酮、O,O-二乙基氢膦双硫代酸酯和氧化铝负载的硼氢化钠混合物进行微波辐照，可以高产率和高对映选择性地合成噻丙烷。
• Stereoselective synthesis of unhindered olefins by 2-fold extrusion reactions
  作者：Luis R. Collazo、Frank S. Guziec

  DOI：10.1021/jo00053a013

  日期：1993.1

  Two-fold extrusion reactions of 1,3,4-thiadiazolines 1 provide a convenient stereoselective route to unhindered Z-olefins. An improved preparation of the thiadiazolines involves reaction of an aldehyde with H2S-hydrazine, followed by in situ oxidation of the intermediate predominantly trans thiadiazolidine 2. Stereospecific extrusion of nitrogen yields the cis-thiirane which upon treatment with triphenylphosphine affords the corresponding Z-alkene in good yields.