(1R,3R)-trans-2-carbethoxy-1,3-dithiane 1,3-dioxide | 144375-59-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: (1R,3R)-trans-2-carbethoxy-1,3-dithiane 1,3-dioxide
• 英文别名: (R,R)-2-carbethoxy-1,3-dithiane-trans-1,3-dioxide；ethyl (1R,3R)-1,3-dioxo-1,3-dithiane-2-carboxylate
• CAS: 144375-59-7
• 化学式: C₇H₁₂O₄S₂
• 分子量: 224.302
• InChiKey: DNSIQDBMMXMYAN-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  98.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1R,3R)-trans-2-carbethoxy-1,3-dithiane 1,3-dioxide 在 盐酸 、 sodium hydroxide 作用下， 以 水 为溶剂， 反应 17.0h， 以83%的产率得到trans-1(RS)-3(RS)-1,3-Dithiane 1,3-dioxide
  参考文献：
  名称：

  Studies on the Asymmetric Oxidation of Ester Derivatives of 1,3-Dithiane-2-carboxylates. Asymmetric Synthesis of trans-1,3-Dithiane 1,3-Dioxide

  摘要：

  Asymmetric oxidation of a range of 1,3-dithianes was studied using the Kagan protocol [CHP (4 equiv), (+)-DET (2 equiv), Ti(OiPr)(4) (1 equiv), and H2O (1 equiv) at -35 degrees C for 48 h]. 1,3-Dithiane itself gave monoxide (30% eel and the trans bis-sulfoxide (59% eel but with low enantioselectivity. In contrast, ester derivatives (Me, Et, t-Bu, Ph) of 1,3-dithiane-2-carboxylates gave monoxides (80-95% eel and trans bis-sulfoxides (> 97% ee) in high enantioselectivity. Optimum conditions for the oxidation of ethyl 1,3-dithiane-2-carboxylate required the Modena protocol [CHP (4 equiv), (+)DET (2 equiv), and Ti(OiPr)(4) (0.5 equiv) at -22 degrees C for 24 h], and this gave the trans bis-sulfoxide in 60% yield and high enantioselectivity. The bis-sulfoxides were found to be acid sensitive and required rapid workup and purification for optimum yields. The differences between the Modena and Kagan oxidants are discussed together with a discussion on the origin of the high enantio- and diastereoselectivity of the reaction. Finally, hydrolysis and decarboxylation furnished trans-1,3-dithiane 1,3-dioxide.

  DOI：

  10.1021/jo9807971
• 作为产物：
  描述：

  1,3-二噻烷-2-甲酸乙酯 在 titanium(IV) isopropylate 、 L-(+)-酒石酸二乙酯 、 过氧化氢异丙苯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 生成 (1R,3R)-trans-2-carbethoxy-1,3-dithiane 1,3-dioxide 、 (R)-1,1,3-Trioxo-1λ⁶,3λ⁴-[1,3]dithiane-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Chiral bisfunctionalization of substrates: a powerful strategy for the asymmetric synthesis of C2 symmetric compounds and its application to the synthesis of enantiomerically pure trans-1,3-dithiane 1,3-dioxide

  摘要：

  We have found that the chiral, bisfunctionalization of substrates is a powerful strategy for the preparation Of C2 symmetric compounds with very high enantiomeric excess, and by applying this strategy with the Modena method for the asymmetric oxidation of sulfides we have prepared (1R,3R)-1,3-dithiane 1,3-dioxide (1) in enantiomerically pure form.

  DOI：

  10.1021/jo00050a008

文献信息

• Studies on the Asymmetric Oxidation of Ester Derivatives of 1,3-Dithiane-2-carboxylates. Asymmetric Synthesis of <i>trans</i>-1,3-Dithiane 1,3-Dioxide
  作者：Varinder K. Aggarwal、Blanca N. Esquivel-Zamora、Graham R. Evans、Elfyn Jones

  DOI：10.1021/jo9807971

  日期：1998.10.1

  Asymmetric oxidation of a range of 1,3-dithianes was studied using the Kagan protocol [CHP (4 equiv), (+)-DET (2 equiv), Ti(OiPr)(4) (1 equiv), and H2O (1 equiv) at -35 degrees C for 48 h]. 1,3-Dithiane itself gave monoxide (30% eel and the trans bis-sulfoxide (59% eel but with low enantioselectivity. In contrast, ester derivatives (Me, Et, t-Bu, Ph) of 1,3-dithiane-2-carboxylates gave monoxides (80-95% eel and trans bis-sulfoxides (> 97% ee) in high enantioselectivity. Optimum conditions for the oxidation of ethyl 1,3-dithiane-2-carboxylate required the Modena protocol [CHP (4 equiv), (+)DET (2 equiv), and Ti(OiPr)(4) (0.5 equiv) at -22 degrees C for 24 h], and this gave the trans bis-sulfoxide in 60% yield and high enantioselectivity. The bis-sulfoxides were found to be acid sensitive and required rapid workup and purification for optimum yields. The differences between the Modena and Kagan oxidants are discussed together with a discussion on the origin of the high enantio- and diastereoselectivity of the reaction. Finally, hydrolysis and decarboxylation furnished trans-1,3-dithiane 1,3-dioxide.
• Chiral bisfunctionalization of substrates: a powerful strategy for the asymmetric synthesis of C2 symmetric compounds and its application to the synthesis of enantiomerically pure trans-1,3-dithiane 1,3-dioxide
  作者：Varinder K. Aggarwal、Graham Evans、Eduardo Moya、James Dowden

  DOI：10.1021/jo00050a008

  日期：1992.11

  We have found that the chiral, bisfunctionalization of substrates is a powerful strategy for the preparation Of C2 symmetric compounds with very high enantiomeric excess, and by applying this strategy with the Modena method for the asymmetric oxidation of sulfides we have prepared (1R,3R)-1,3-dithiane 1,3-dioxide (1) in enantiomerically pure form.