(p-Tolyl)[[(1R,6S)-6beta-(3-acetoxypropyl)bicyclo[4.1.0]heptan]-1beta-yl] sulfide

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (p-Tolyl)[[(1R,6S)-6beta-(3-acetoxypropyl)bicyclo[4.1.0]heptan]-1beta-yl] sulfide
• 英文别名: 3-[(1S,6R)-6-(4-methylphenyl)sulfanyl-1-bicyclo[4.1.0]heptanyl]propyl acetate
• 化学式: C₁₉H₂₆O₂S
• 分子量: 318.5
• InChiKey: GGHHPPPTUPVSTH-RBUKOAKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 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：

  (p-Tolyl)[[(1R,6S)-6beta-(3-acetoxypropyl)bicyclo[4.1.0]heptan]-1beta-yl] sulfide 、 mercury(II) trifluoroacetate 在 sodium acetate 、 sodium chloride 作用下， 以 二氯甲烷 为溶剂， 以84%的产率得到[(1R)-1-(3-acetyloxypropyl)-2-(4-methylphenyl)sulfinylcyclohex-2-en-1-yl]methyl-chloromercury
  参考文献：
  名称：

  A sulfur-assisted regioselective α-functionalization of cyclopropyl sulfides. Synthetic applications of homoallyl anion synthon

  摘要：

  由环丙基硫醚 7 和三氟乙酸汞 (II) 生成的δ,δ-不饱和δ-亚磺酰基或亚磺烷基汞氯化物 5 和 15 被证明是同烯丙基阴离子合成物；这些化合物在与几种亲电物反应时再生成δ-官能化环丙基硫醚。

  DOI：

  10.1039/c39920000192

文献信息

• Regioselective Functionalization of the Methylene Group Adjacent to Cyclopropyl Sulfide via Mercury(II)-Mediated Regioselective Ring-Opening Reaction.
  作者：Yoshiji TAKEMOTO、Taiichi OHRA、Yasuhiro YONETOKU、Chuzo IWATA

  DOI：10.1248/cpb.43.1859

  日期：——

  A regioselective bond-cleavage of the cyclopropyl sulfide (2) was performed with mercury(II) salt to supply the homoallyl anion synthon (3) bearing two reactive sites at the α and δ positions. The reaction of 3 with n-Bu3SnH and I2 gave α-functionalized products (8 and 9, respectively). On the other hand, recyclization of 3 into δ-functionalized cyclopropyl sulfides (2, 12, 13) was accomplished by treatment with several electrophiles (H+, D+, allyl iodide).Moreover, the synthesis of δ-oxygenated cyclopropyl sulfide (15) was achieved by the additive Pummerer reaction of the γ, δ-unsaturated γ-sulfinyl alkylmercury chloride (14) which was obtained by m-chloroperbenzoic acid oxidation of 3.

  环丙基硫醚（2）与汞（II）盐发生区域选择性键断裂反应，生成α和δ位上带有两个反应位点的均二烯丙基阴离子合成体（3）。3与n-Bu3SnH和I2反应生成α官能化产物（分别为8和9）。另一方面，3与几种亲电试剂（H+、D+、碘代烯丙基）反应，可循环生成δ官能化的环丙基硫醚（2、12、13）。此外，γ、δ-不饱和γ-亚磺酰烷基氯化汞（14）通过间氯过氧苯甲酸氧化3生成，通过Pummerer加成反应合成δ-氧化的环丙基硫醚（15）。
• Takemoto Yoshiji, Ohra Taiichi, Koike Hiroki, Furuse Syun-ichirou, Iwata +, J. Org. Chem, 59 (1994) N 17, S 4727-4729
  作者：Takemoto Yoshiji, Ohra Taiichi, Koike Hiroki, Furuse Syun-ichirou, Iwata +

  DOI：——

  日期：——
• Chirality Preservation of a Cation-Radical Intermediate. Tandem Oxidative Ring Expansion-Cyclization Reaction of Optically Active Bicyclo[4.1.0]heptyl Sulfides
  作者：Yoshiji Takemoto、Taiichi Ohra、Hiroki Koike、Syun-ichirou Furuse、Chuzo Iwata、Hirofumi Ohishi

  DOI：10.1021/jo00096a010

  日期：1994.8

  Asymmetric synthesis of 1-oxaspiro[4.6]undecan-7-one and spiro[4.6]undecanes has been achieved by a regio- and stereoselective tandem oxidative ring expansion-cyclization reaction of chiral bicyclo[4.1.0]heptyl sulfides bearing an alcohol or electron-rich olefin in the C-6 side chain via a cation radical intermediate.
• A sulfur-assisted regioselective α-functionalization of cyclopropyl sulfides. Synthetic applications of homoallyl anion synthon
  作者：Yoshiji Takemoto、Taiichi Ohra、Yasuhiro Yonetoku、Takeshi Imanishi、Chuzo Iwata

  DOI：10.1039/c39920000192

  日期：——

  γ,δ-Unsaturated γ-sulfenyl or sulfinlalkylmercury chlorides 5 and 15, generated from the cyclopropyl sulfide 7 and mercury (II) trifluoroacetate, were demonstrated to be homoallyl anion synthons; these compounds recyclized into the α-functionalized cyclopropyl sulfide on reaction with several electrophiles.

  由环丙基硫醚 7 和三氟乙酸汞 (II) 生成的δ,δ-不饱和δ-亚磺酰基或亚磺烷基汞氯化物 5 和 15 被证明是同烯丙基阴离子合成物；这些化合物在与几种亲电物反应时再生成δ-官能化环丙基硫醚。