3-<(1S,6R)-6-(p-tolylthio)bicyclo<4.1.0>hept-1-yl>prop-1-ene | 169560-24-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3-<(1S,6R)-6-(p-tolylthio)bicyclo<4.1.0>hept-1-yl>prop-1-ene
• 英文别名: (1R,6S)-1-(4-methylphenyl)sulfanyl-6-prop-2-enylbicyclo[4.1.0]heptane
• CAS: 169560-24-1
• 化学式: C₁₇H₂₂S
• 分子量: 258.428
• InChiKey: VJZYVQBQLYTRSD-IAGOWNOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-<(1S,6R)-6-(p-tolylthio)bicyclo<4.1.0>hept-1-yl>prop-1-ene 在 jones reagent 、 dimethyl sulfide borane 、 双氧水 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 溶剂黄146 、 丙酮 为溶剂， 反应 12.33h， 生成 3-<(1R,6R)-6-(p-tolylsulfonyl)bicyclo<4.1.0>hept-1-yl>propionic acid
  参考文献：
  名称：

  Asymmetric Cyclopropanation by Reaction of a .GAMMA.-Chloromethylated Chiral Vinylic Sulfoxide with Allylmagnesium Bromide.

  摘要：

  通过与烯丙基溴化镁的迈克尔加成反应，一种在 γ 位带有离去基团的光学活性乙烯基亚砜被立体选择性地转化为手性环丙烷。迈克尔诱导的闭环反应需要溴化烯丙基镁作为不亲和基和氯化物作为离去基团才能实现高非对映选择性。通过 X 射线分析确认了环加合物的绝对立体化学性质。

  DOI：

  10.1248/cpb.43.571
• 作为产物：
  描述：

  (1R,6S)-1-(4-methylphenyl)sulfinyl-6-prop-2-enylbicyclo[4.1.0]heptane 在 三氟乙酸酐 、 sodium iodide 作用下， 以 丙酮 为溶剂， 以100%的产率得到3-<(1S,6R)-6-(p-tolylthio)bicyclo<4.1.0>hept-1-yl>prop-1-ene
  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）。
• Novel asymmetric cyclopropanation utilizing sulfinyl chirality: application to construction of a spiro [4.5]decane system
  作者：Takeshi Imanishi、Taiichi Ohra、Kenji Sugiyama、Yoko Ueda、Yoshiji Takemoto、Chuzo Iwata

  DOI：10.1039/c39920000269

  日期：——

  An optically active vinylic sulfoxide is stereoselectiviely transformed into a chiral cyclopropane by means of a Michael addition reaction with an allyl Grignard reagent, and using this novel cyclopropanation, assmmetric construction of a spiro [4.5] decane is achieved.

  通过与烯丙基格氏试剂发生迈克尔加成反应，一种光学活性乙烯基亚砜被立体选择性地转化为手性环丙烷，并利用这种新型环丙烷化反应，按比例构建了螺[4.5]癸烷。
• Asymmetric Cyclopropanation by Reaction of a .GAMMA.-Chloromethylated Chiral Vinylic Sulfoxide with Allylmagnesium Bromide.
  作者：Yoshiji TAKEMOTO、Taiichi OHRA、Kenji SUGIYAMA、Takeshi IMANISHI、Chuzo IWATA

  DOI：10.1248/cpb.43.571

  日期：——

  An optically active vinylic sulfoxide bearing a leaving group at the γ-position was stereoselectively transformed into a chiral cyclopropane by means of a Michael addition with an allylmagnesium bromide. The Michael induced ring-closure reaction requires both allylmagnesium bromide as a uncleophile and chloride as a leaving group for high diastereoselectivity. The absolute stereochemistry of the cycloadduct was confirmed by X-ray analysis.

  通过与烯丙基溴化镁的迈克尔加成反应，一种在 γ 位带有离去基团的光学活性乙烯基亚砜被立体选择性地转化为手性环丙烷。迈克尔诱导的闭环反应需要溴化烯丙基镁作为不亲和基和氯化物作为离去基团才能实现高非对映选择性。通过 X 射线分析确认了环加合物的绝对立体化学性质。
• 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。