1-(2'-Tetrahydropyranyl)-3-(phenylthio)propanone | 153757-39-2

• 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'-Tetrahydropyranyl)-3-(phenylthio)propanone
• 英文别名: 1-(Oxan-2-yl)-3-phenylsulfanylpropan-1-one
• CAS: 153757-39-2
• 化学式: C₁₄H₁₈O₂S
• 分子量: 250.362
• InChiKey: JHAIFYSOQHETTI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  1-(2'-Tetrahydropyranyl)-3-(phenylthio)propanone 在 zinc(II) tetrahydroborate 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 (1R*,2'S*)-3-(Phenylthio)-1-(2'-tetrahydropyranyl)-1-propanol 、 (1R*,2'R*)-3-(Phenylthio)-1-(2'-tetrahydropyranyl)-1-propanol
  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'-Tetrahydropyranyl)-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

• Cerium(III) chloride remarkably increases the rates of formation and yields of ketones in the reaction of lithium carboxylates with organolithiums
  作者：Yoonmo Ahn、Theodore Cohen

  DOI：10.1016/s0040-4039(00)76511-7

  日期：1994.1

  ketones in the reaction of organolithiums with lithium carboxylates. The CeIII suppresses the enolization of the lithium carboxylate, previously unrecognized as a competing reaction except in special cases, and the formation of tertiary alcohols. One of the reasons for the latter effect is a surprising increase in the rate of addition of the organometallic to the lithium carboxylate in the presence

  CeCl 3的存在大大提高了有机锂与羧酸锂反应中酮的产率。Ce III抑制了羧酸锂的烯醇化作用，该反应以前未被公认是竞争性反应，除非在特殊情况下，还可以抑制叔醇的形成。后一种作用的原因之一是在Ce III的存在下，有机金属与羧酸锂的加成速率惊人地增加。
• 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.