1-(2'-Tetrahydrofuranyl)-3-(phenylthio)propanone | 157756-87-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-(2'-Tetrahydrofuranyl)-3-(phenylthio)propanone
• 英文别名: 1-(Oxolan-2-yl)-3-phenylsulfanylpropan-1-one
• CAS: 157756-87-1
• 化学式: C₁₃H₁₆O₂S
• 分子量: 236.335
• InChiKey: FUSGXMOGQWXACL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cerium,dichloromethane 、 1-(2'-Tetrahydrofuranyl)-3-(phenylthio)propanone 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (2R*,2'S*)-4-(Phenylthio)-2-(2'-tetrahydrofuranyl)-2-butanol 、 (2R*,2'R*)-4-(Phenylthio)-2-(2'-tetrahydrofuranyl)-2-butanol
  参考文献：
  名称：

  A General Diastereoselective Synthesis of Spiroacetals Related to Those in Ionophores via the Reaction of Lactones with Cerium(III) .gamma.-Cerioalkoxide. MAD Reverses the Diastereoselectivity of the Addition of Methylmetallics to a .beta.-Keto Ether

  摘要：

  The following steps constitute a fairly general and stereoselective synthesis of spiroacetals. 1. Thiophenol is added to acrylic acid. 2. The latter is treated consecutively with butyllithium, CeCl3, and an organolithium compound. 3. The resulting 3-(phenylthio) ketone is either reduced in the presence of zinc ion to yield mainly one diastereomer or treated with methyllithium or methylmagnesium chloride in the presence or absence of methylaluminum bis(2,6-di-tert-butyl-4-mthylphenoxide) (MAD, 25) to yield selectively either of two diastereomeric 3-(phenylthio) alcohols. 4. The alcohol is treated with butyllithium, lithium 4,4'-di-tert-butylbiphenylide (LDBB), and CeCl3, to yield a cerium(III) gamma-cerioalkoxide, which is added to a lactone, the reaction being quenched with acid. In the addition to the keto ether in the absence of MAD, methyllithium or methylmagnesium chloride give very predominantly the erythro alcohol, presumably via Cram's chelate model, while in the presence of excess MAD, the three product is very predominant, possibly because each oxygen atom is complexed with the bulky aluminum reagent. The methodology is demonstrated by the preparation of diastereomeric spiroacetals related to those found in a number of natural ionophores by using as the reaction partner of the carboxylate salt, alpha-lithio tetrahydrofuran or tetrahydropyran, readily generated by reductive lithiation of the corresponding alpha-(phenylthio) heterocycle with LDBB, and by employing methylmetallics rather than reducing agents for the reaction with the ketone.

  DOI：

  10.1021/jo00090a036
• 作为产物：
  描述：

  3-苯硫基丙酸 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 1-(2'-Tetrahydrofuranyl)-3-(phenylthio)propanone
  参考文献：
  名称：

  A General Diastereoselective Synthesis of Spiroacetals Related to Those in Ionophores via the Reaction of Lactones with Cerium(III) .gamma.-Cerioalkoxide. MAD Reverses the Diastereoselectivity of the Addition of Methylmetallics to a .beta.-Keto Ether

  摘要：

  The following steps constitute a fairly general and stereoselective synthesis of spiroacetals. 1. Thiophenol is added to acrylic acid. 2. The latter is treated consecutively with butyllithium, CeCl3, and an organolithium compound. 3. The resulting 3-(phenylthio) ketone is either reduced in the presence of zinc ion to yield mainly one diastereomer or treated with methyllithium or methylmagnesium chloride in the presence or absence of methylaluminum bis(2,6-di-tert-butyl-4-mthylphenoxide) (MAD, 25) to yield selectively either of two diastereomeric 3-(phenylthio) alcohols. 4. The alcohol is treated with butyllithium, lithium 4,4'-di-tert-butylbiphenylide (LDBB), and CeCl3, to yield a cerium(III) gamma-cerioalkoxide, which is added to a lactone, the reaction being quenched with acid. In the addition to the keto ether in the absence of MAD, methyllithium or methylmagnesium chloride give very predominantly the erythro alcohol, presumably via Cram's chelate model, while in the presence of excess MAD, the three product is very predominant, possibly because each oxygen atom is complexed with the bulky aluminum reagent. The methodology is demonstrated by the preparation of diastereomeric spiroacetals related to those found in a number of natural ionophores by using as the reaction partner of the carboxylate salt, alpha-lithio tetrahydrofuran or tetrahydropyran, readily generated by reductive lithiation of the corresponding alpha-(phenylthio) heterocycle with LDBB, and by employing methylmetallics rather than reducing agents for the reaction with the ketone.

  DOI：

  10.1021/jo00090a036

文献信息

• A General Diastereoselective Synthesis of Spiroacetals Related to Those in Ionophores via the Reaction of Lactones with Cerium(III) .gamma.-Cerioalkoxide. MAD Reverses the Diastereoselectivity of the Addition of Methylmetallics to a .beta.-Keto Ether
  作者：Yoonmo Ahn、Theodore Cohen

  DOI：10.1021/jo00090a036

  日期：1994.6

  The following steps constitute a fairly general and stereoselective synthesis of spiroacetals. 1. Thiophenol is added to acrylic acid. 2. The latter is treated consecutively with butyllithium, CeCl3, and an organolithium compound. 3. The resulting 3-(phenylthio) ketone is either reduced in the presence of zinc ion to yield mainly one diastereomer or treated with methyllithium or methylmagnesium chloride in the presence or absence of methylaluminum bis(2,6-di-tert-butyl-4-mthylphenoxide) (MAD, 25) to yield selectively either of two diastereomeric 3-(phenylthio) alcohols. 4. The alcohol is treated with butyllithium, lithium 4,4'-di-tert-butylbiphenylide (LDBB), and CeCl3, to yield a cerium(III) gamma-cerioalkoxide, which is added to a lactone, the reaction being quenched with acid. In the addition to the keto ether in the absence of MAD, methyllithium or methylmagnesium chloride give very predominantly the erythro alcohol, presumably via Cram's chelate model, while in the presence of excess MAD, the three product is very predominant, possibly because each oxygen atom is complexed with the bulky aluminum reagent. The methodology is demonstrated by the preparation of diastereomeric spiroacetals related to those found in a number of natural ionophores by using as the reaction partner of the carboxylate salt, alpha-lithio tetrahydrofuran or tetrahydropyran, readily generated by reductive lithiation of the corresponding alpha-(phenylthio) heterocycle with LDBB, and by employing methylmetallics rather than reducing agents for the reaction with the ketone.