3,3-Bis(ethylsulfanyl)-1-(4-methoxyphenyl)-4-(2-phenylethynyl)azetidin-2-one | 159051-06-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: 3,3-Bis(ethylsulfanyl)-1-(4-methoxyphenyl)-4-(2-phenylethynyl)azetidin-2-one
• CAS: 159051-06-6
• 化学式: C₂₂H₂₃NO₂S₂
• 分子量: 397.562
• InChiKey: FBHIAWOICIBKAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  80.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3-Bis(ethylsulfanyl)-1-(4-methoxyphenyl)-4-(2-phenylethynyl)azetidin-2-one 在 碘 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到(1S,5S)-1-Ethylsulfanyl-4-iodo-6-(4-methoxy-phenyl)-3-phenyl-2-thia-6-aza-bicyclo[3.2.0]hept-3-en-7-one
  参考文献：
  名称：

  Synthesis of Novel .beta.-Lactam Core Structures Related to the Penam and Penem Antibiotics

  摘要：

  The synthesis of a structurally new class of penicillin- and penem-type ring systems is described which is based on a sequential imine-ketene cycloaddition reaction and halogen-induced sulfide cyclization process.

  DOI：

  10.1021/jo00099a007
• 作为产物：
  描述：

  苯丙炔醛 在 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 3,3-Bis(ethylsulfanyl)-1-(4-methoxyphenyl)-4-(2-phenylethynyl)azetidin-2-one
  参考文献：
  名称：

  Synthesis of Novel .beta.-Lactam Core Structures Related to the Penam and Penem Antibiotics

  摘要：

  The synthesis of a structurally new class of penicillin- and penem-type ring systems is described which is based on a sequential imine-ketene cycloaddition reaction and halogen-induced sulfide cyclization process.

  DOI：

  10.1021/jo00099a007

文献信息

• Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Xiao-Feng Ren、Edward Turos、Charles H. Lake、Melvyn Rowen Churchill

  DOI：10.1021/jo00125a038

  日期：1995.10

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.
• Synthesis of Novel .beta.-Lactam Core Structures Related to the Penam and Penem Antibiotics
  作者：Xiao-Feng Ren、Edward Turos

  DOI：10.1021/jo00099a007

  日期：1994.10

  The synthesis of a structurally new class of penicillin- and penem-type ring systems is described which is based on a sequential imine-ketene cycloaddition reaction and halogen-induced sulfide cyclization process.
• Studies on Nonconventionally Fused Bicyclic β-Lactams
  作者：Xiao-Feng Ren、Monika I. Konaklieva、Hongchang Shi、Sonja Dickey、Daniel V. Lim、Javier Gonzalez、Edward Turos

  DOI：10.1021/jo9811219

  日期：1998.11.1

  Described in this article are studies of structurally novel [3.2.0]bicyclic beta-lactam ring systems that are isomeric to those of the penicillin, penem, and clavulanic acid families of antibiotics, but which have the lactam functionality arranged in alternative orientations within the four-membered ring. Semiempirical calculations indicate that the thermodynamic stabilities of the three alternative isomeric ring systems are similar to that of the classical penam or penem structure, and ab initio methods reveal that the LUMO energies of the two C-fused ring structures 11 and 12 are more than 1 eV lower than that of 2-azetidinone, but 0.22 to 0.73 eV higher than that of the penem ring 13. The LUMO energy of the N-S fused penem structure 14 is about 0.2 eV lower than that of 13. These studies also suggest that the N-fused bicyclic beta-lactams are considerably more electrophilic than the corresponding C-fused compounds. Several of the new heterocyclic rings were synthesized using a two-step cyclization strategy to assemble the bicyclic core. First, the beta-lactam ring was created by a Staudinger reaction of an acid chloride and alpha,beta-unsaturated imine, and the sulfur heterocycle was closed through a halogen-promoted cyclization reaction of a sulfur substituent onto a neighboring alkenyl or alkynyl side chain. Using palladium catalysis, iodopenem adducts 18, 31a, and 56a were converted to vinyl- and heteroaryl-substituted derivatives, carboxylic esters, and carboxylic acids. Four of the bicyclic beta-lactams prepared in this study (58b, 80, 87, and 89) showed weak levels of activity against Staphylococcus aureus or Vibrio cholerae.