(S,E)-3-(p-tolylsulfinyl)-3-pentene-2-one | 207983-95-7

• 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: (S,E)-3-(p-tolylsulfinyl)-3-pentene-2-one
• 英文别名: (E)-3-[(S)-(4-methylphenyl)sulfinyl]pent-3-en-2-one
• CAS: 207983-95-7
• 化学式: C₁₂H₁₄O₂S
• 分子量: 222.308
• InChiKey: QMKWYEVAYRBMIX-XANQCZFBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S,E)-3-(p-tolylsulfinyl)-3-pentene-2-one 在 ammonium acetate 、 sodium hydride 作用下， 以 甲醇 为溶剂， 生成 methyl (4R,S_S)-1,4-dihydro-2,4,6-trimethyl-5-(p-tolylsulfinyl)pyridine-3-carboxylate
  参考文献：
  名称：

  Novel and chiral hantzsch-type 1,4-dihydropyridines having A p-tolylsulfinyl group. Synthesis and biological activities as calcium channel antagonists.

  摘要：

  新型汉茨型 4-芳基和 4-甲基-1, 4-二氢吡啶 3 的 C-4 立体异构体均在 C-5 位上带有对甲苯磺酰基，这些立体异构体以 α-亚磺酰基烯酮 6 为起点，以光学纯度的形式高效合成，α-亚磺酰基烯酮 6 很容易从 (-)-(S)- 对甲苯磺酸盐 (4) 中获得。研究发现，C-4 处的立体化学在很大程度上决定了这些化合物作为钙通道拮抗剂的生物活性。

  DOI：

  10.1248/cpb.43.711
• 作为产物：
  描述：

  (E)-3-((S)-Toluene-4-sulfinyl)-pent-3-en-2-ol 以98%的产率得到(S,E)-3-(p-tolylsulfinyl)-3-pentene-2-one
  参考文献：
  名称：

  Novel and chiral hantzsch-type 1,4-dihydropyridines having A p-tolylsulfinyl group. Synthesis and biological activities as calcium channel antagonists.

  摘要：

  新型汉茨型 4-芳基和 4-甲基-1, 4-二氢吡啶 3 的 C-4 立体异构体均在 C-5 位上带有对甲苯磺酰基，这些立体异构体以 α-亚磺酰基烯酮 6 为起点，以光学纯度的形式高效合成，α-亚磺酰基烯酮 6 很容易从 (-)-(S)- 对甲苯磺酸盐 (4) 中获得。研究发现，C-4 处的立体化学在很大程度上决定了这些化合物作为钙通道拮抗剂的生物活性。

  DOI：

  10.1248/cpb.43.711

文献信息

• Radical β-addition to acyclic α-(arylsulfinyl) enones: Pummerer-type rearrangement
  作者：Nobuyuki Mase、Yoshihiko Watanabe、Yoshio Ueno、Takeshi Toru

  DOI：10.1039/a800828k

  日期：——

  The reaction of (S,E)-3-(p-tolylsulfinyl)pent-3-en-2-one with an isopropyl radical, generated from isopropyl iodide and triethylborane, gives the non-stereoselective addition product and an unexpected α-(arylsulfanyl) enone which is formed through a radical addition and subsequent Pummerer-type rearrangement. The formation of the α-(arylsulfanyl) enone depends upon the additives used as well as the aryl group on the sulfur.

  (S,E)-3-(对甲苯基亚磺酰基)戊-3-烯-2-酮与由碘化异丙基和三乙基硼烷生成的异丙基发生反应，得到非立体选择性加成产物和意外的δ-（芳基硫酰基）烯酮，后者是通过自由基加成和随后的普默尔型重排形成的。δ-（芳基硫基）烯酮的形成取决于所使用的添加剂以及硫上的芳基。
• Photo-Induced Intermolecular Radical<i>β</i>-Addition to Chiral<i>α</i>-(Arylsulfinyl) Enones
  作者：Nobuyuki Mase、Yoshihiko Watanabe、Takeshi Toru

  DOI：10.1246/bcsj.71.2957

  日期：1998.12

  The reactions of α-(arylsulfinyl) enones with alkyl radicals having a hydroxy or acetal group were examined under photo-irradiation in the presence of benzophenone. High diastereoselectivity was observed in the photo-induced radical reaction of 2-(arylsulfinyl)-2-cyclopentenones having a bulky aryl group, such as the 2,4,6-triisopropylphenyl or 2,4,6-trimethylphenyl group. The photo-induced reaction of 3-[(2,4,6-triisopropylphenyl)sulfinyl]-3-pentene-2-one in 1,3-dioxolane also gave a single diastereomer of the 1,3-dioxolan-2-yl adduct.

  在二苯甲酮存在下，在光照射下检查了α-（芳基亚磺酰基）烯酮与具有羟基或缩醛基团的烷基的反应。在具有大芳基（例如2,4,6-三异丙基苯基或2,4,6-三甲基苯基）的2-（芳基亚磺酰基）-2-环戊烯酮的光诱导自由基反应中观察到高非对映选择性。 3-[(2,4,6-三异丙基苯基)亚磺酰基]-3-戊烯-2-酮在1,3-二氧戊环中的光诱导反应也产生了1,3-二氧戊环-2-基的单一非对映体加合物。
• Novel and Regioselective Lithiation of the Unsymmetrical Hantzsch-Type 1,4-Dihydropyridine by Participation of the Neighboring Sulfinyl Group.
  作者：Kazuyuki MIYASHITA、Masahiro NISHIMOTO、Hidenobu MURAFUJI、Satoshi OBIKA、Takeshi IMANISHI

  DOI：10.1248/cpb.44.457

  日期：——

  The C-6 methyl group of methyl (4R, SS)-2, 4, 6-trimethyl-5-(p-tolylsulfinyl)-1, 4-dihydropyridine-3-carboxylate (2) was found to be regioselectively lithiated by participation of the neighboring sulfinyl group, giving rise to the 6-modified Hantzsch-type compounds by treatment with n-butyllihium and the electrophiles.

  研究发现，(4R, SS)-2, 4, 6-三甲基-5-（对甲苯基亚磺酰基）-1, 4-二氢吡啶-3-羧酸甲酯（2）的 C-6 甲基在邻近亚磺酰基的参与下发生了区域选择性光化，从而在正丁基锂和亲电物的处理下生成了 6 改性的汉茨奇型化合物。
• Studies on novel and chiral 1,4-dihydropyridines. V. Hantzsch-type 1,4-dihydropyridines having a chiral sulfinyl group: Syntheses, structures, and biological activity as a calcium channel antagonist
  作者：Kazuyuki Miyashita、Masahiro Nishimoto、Tetsuya Ishino、Hidenobu Murafuji、Satoshi Obika、Osamu Muraoka、Takeshi Imanishi

  DOI：10.1016/s0040-4020(97)00155-5

  日期：1997.3

  4-Aryl and 4-methyl substituted Hantzsch-type 1,4-dihydropyridines having a chiral solfinyl group as an electron-withdrawing group were successfully synthesized in an optically active form from beta-ketosulfoxides via two routes. The relationship between calcium channel antagonist activity and the structures of 4-aryl derivatives was also studied. (C) 1997 Elsevier Science Ltd.
• Novel and chiral hantzsch-type 1,4-dihydropyridines having A p-tolylsulfinyl group. Synthesis and biological activities as calcium channel antagonists.
  作者：Kazuyuki MIYASHITA、Masahiro NISHIMOTO、Tetsuya ISHINO、Satoshi OBIKA、Takeshi IMANISHI

  DOI：10.1248/cpb.43.711

  日期：——

  Both C-4 stereoisomers of novel Hantzch-type 4-aryl- and 4-methyl-1, 4-dihydropyridines 3 having a p-tolylsulfinyl group at C-5 were efficiently synthesized in optically pure forms starting from the α-sulfinyl enones 6 which could be easily obtained from (-)-menthyl (S)-p-tolylsulfinate (4). The stereochemistry at C-4 was found to be largely responsible for the biological activities as calcium channel antagonists of these compounds.

  新型汉茨型 4-芳基和 4-甲基-1, 4-二氢吡啶 3 的 C-4 立体异构体均在 C-5 位上带有对甲苯磺酰基，这些立体异构体以 α-亚磺酰基烯酮 6 为起点，以光学纯度的形式高效合成，α-亚磺酰基烯酮 6 很容易从 (-)-(S)- 对甲苯磺酸盐 (4) 中获得。研究发现，C-4 处的立体化学在很大程度上决定了这些化合物作为钙通道拮抗剂的生物活性。