(E)-2,2-dimethyl-7-phenyl-5-phenylthiomethyl-6-hepten-3-one | 137346-07-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-2,2-dimethyl-7-phenyl-5-phenylthiomethyl-6-hepten-3-one
• 英文别名: (E)-2,2-dimethyl-7-phenyl-5-(phenylsulfanylmethyl)hept-6-en-3-one
• CAS: 137346-07-7
• 化学式: C₂₂H₂₆OS
• 分子量: 338.514
• InChiKey: USEJDQZGDLNKND-CCEZHUSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.11
• 重原子数：
  24.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  茴香硫醚 在 正丁基锂 、 四甲基乙二胺 、 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 (E)-2,2-dimethyl-7-phenyl-5-phenylthiomethyl-6-hepten-3-one
  参考文献：
  名称：

  A Highly Regioselective Reaction of Allylic Acetates with Silylated Carbon Nucleophiles Directed by a Sulfenyl Group. Scope, Limitation, and Mechanistic Aspects

  摘要：

  α-(Sulfenyl甲基)烯丙基醋酸盐在催化量的TMSOTf存在下，与硅烷化的碳亲核试剂反应，以中等至良好的产率和高度区域选择性在硫代甲基的α-位置上进行取代。对中间体阳离子物种的理论计算表明，环硫鎓离子是一种稳定形式；观察到的区域选择性定性地基于阳离子的LUMO系数进行合理化。还展示了一些产物的转化。

  DOI：

  10.1246/bcsj.66.848

文献信息

• A highly regioselective reaction of allylic acetates with silylated carbon nucleophiles directed by a sulfenyl group
  作者：Kazuaki Kudo、Kazuhiko Saigo、Yukihiko Hashimoto、Hitoshi Houchigai、Masaki Hasegawa

  DOI：10.1016/s0040-4039(00)92157-9

  日期：——

  (alpha-Sulfenylmethyl)allyl acetates reacted with silylated carbon nucleophiles in the presence of a catalytic amount of a Lewis acid to give mainly alpha-adducts at the sulfenylmethyl group in moderate to good yields with high regioselectivity. The reaction may proceed via episulfonium ion intermediates.
• A Highly Regioselective Reaction of Allylic Acetates with Silylated Carbon Nucleophiles Directed by a Sulfenyl Group. Scope, Limitation, and Mechanistic Aspects
  作者：Kazuaki Kudo、Yukihiko Hashimoto、Hitoshi Houchigai、Masaki Hasegawa、Kazuhiko Saigo

  DOI：10.1246/bcsj.66.848

  日期：1993.3

  α-(Sulfenylmethyl)allyl acetates reacted with silylated carbon nucleophiles in the presence of a catalytic amount of TMSOTf to give products substituted at the α-position of the sulfenylmethyl group in moderate to good yields with high regioselectivity. The theoretical calculation on an intermediate cationic species indicated that an episulfonium ion was a stable form; the observed regioselectivity was rationalized qualitatively on the basis of the coefficients of LUMO of the cation. Some transformations of the products were also demonstrated.

  α-(Sulfenyl甲基)烯丙基醋酸盐在催化量的TMSOTf存在下，与硅烷化的碳亲核试剂反应，以中等至良好的产率和高度区域选择性在硫代甲基的α-位置上进行取代。对中间体阳离子物种的理论计算表明，环硫鎓离子是一种稳定形式；观察到的区域选择性定性地基于阳离子的LUMO系数进行合理化。还展示了一些产物的转化。