2-(Phenylthio)-N-(2-propenyl)acetamide | 147949-45-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-(Phenylthio)-N-(2-propenyl)acetamide
• 英文别名: N-allyl(phenylsulfanyl)acetamide；Cambridge id 6166326；2-phenylsulfanyl-N-prop-2-enylacetamide
• CAS: 147949-45-9
• 化学式: C₁₁H₁₃NOS
• mdl: MFCD02576683
• 分子量: 207.296
• InChiKey: UAGUCSGYTBCSLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(Phenylthio)-N-(2-propenyl)acetamide 在 4-二氟化碘甲苯 作用下， 以 二氯甲烷 、 Petroleum ether 为溶剂， 反应 2.0h， 生成 2,2-Bis(phenylthio)-N-(2-propenyl)acetamide
  参考文献：
  名称：

  Fluorination of sulfanyl amides using difluoroiodoarene reagents

  摘要：

  使用高价二氟化碘试剂 1 对一系列含硫酰胺进行了氟化处理，并确定了两种主要的反应途径。头孢菌素酯 2 在硫的α位上有一个杂原子，在二氯甲烷中发生氟化反应，碳-硫键断裂，形成新型氟化β-内酰胺 4。在 α 位上带有抽电子基团的硫化物在类似于经典普默尔反应的过程中发生 α-氟化反应。这种氟-普默尔反应已在一系列简单的 α-苯硫基乙酰胺 14-19 中得到验证。当底物中含有 β 氢时，则采用不同的途径，通过碱性氟化物进行去质子化反应，生成乙烯基硫化物 41-43。当使用过量的氟化试剂时，这些乙烯基硫化物可在新型串联式普默尔-添加剂-普默尔工艺中发生进一步反应，生成 α,β-二氟硫化物 45-47。

  DOI：

  10.1039/b209078c
• 作为产物：
  描述：

  2-chloro-2-(phenylthio)acetyl chloride 在 tris(triphenylphosphine)ruthenium(II) chloride 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 6.0h， 生成 2-(Phenylthio)-N-(2-propenyl)acetamide
  参考文献：
  名称：

  Ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic .alpha.-chloro-.alpha.-thioacetamides. Synthesis of (-)-trachelanthamidine and formal total synthesis of (.+-.)-haemanthidine and (.+-.)-pretazettine

  摘要：

  A new method for the synthesis of five-membered lactams by ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic alpha-chloro-alpha-thioacetamides and the application of the method to the synthesis of the title alkaloids are described. A benzene solution of N-allyl-N-methyl-alpha-chloro-alpha-(phenylthio)acetamide (6) was heated at 140-degrees-C in the presence of RuCl2(PPh3)3 to give alpha-thio-beta-(chloromethyl)-substituted gamma-lactam 8 as a mixture of cis and trans isomers in a ratio of ca. 3:7. NH congener 11, however, gave no cyclization product. Heating chloro sulfides 18 and 19, prepared from L-prolinol, with RuCl2(PPh3)3 afforded bicyclic lactams 20 and 21, respectively. Treatment of 20 with cesium propanoate gave predominantly cyclopropane derivative 25, whereas S-methyl congener 21 provided esters 24 in good yield. Desulfurization of 24 with Raney nickel followed by reduction with LiAlH4 furnished (-)-trachelanthamidine (28). On the other hand, N-(cyclohex-2-en-1-yl) derivative 30, when heated with RuCl2(PPh3)3, afforded octahydroindol-2-ones 31a,b. The formation of 31a,b indicated that the intramolecular addition of the chloro sulfide of 30 to the olefinic bond proceeded in an anti-mode. By contrast, 2-phenyl-substituted derivative 38 gave syn-addition product 39. The difference between the modes of cyclization of 30 and 38 can be explained by assuming the intermediacy of radical 34. When R = H, the chlorine atom attacks the convex face of the fused bicyclic system of 34 to lead to 31a,b, whereas the steric bulk of the angular phenyl group (R = Ph) is apparently sufficient to direct the chlorine atom to the concave face. Heating chloro sulfide 48, prepared in a highly stereocontrolled manner from cyclohexene 42, with RuCl2(PPh3)3 afforded bicyclic lactam 49. Oxidation of 49 with m-CPBA followed by Pummerer rearrangement/hydrolysis gave keto lactam 51, which was dehydrochlorinated with DBU to give olefin 52. LiAlH4 reduction of 52 and acylation with pivaloyl chloride provided ester 54, a key intermediate in Martin's total synthesis of (+/-)-haemanthidine (41) and (+/-)-pretazettine (40).

  DOI：

  10.1021/jo00061a005

文献信息

• Studies on the oxidation and fluorination of α-phenylsulfanylacetamides using difluoroiodotoluene
  作者：Michael F Greaney、William B Motherwell

  DOI：10.1016/s0040-4039(00)00617-1

  日期：2000.6

  alpha-Phenylsulfanylacetamides are fluorinated in the alpha-position when treated with difluoroiodotoluene (DFIT) in a fluoro-Pummerer reaction. For N-phenyl amides an intramolecular Friedel-Crafts reaction may compete and produce heterocycles. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic .alpha.-chloro-.alpha.-thioacetamides. Synthesis of (-)-trachelanthamidine and formal total synthesis of (.+-.)-haemanthidine and (.+-.)-pretazettine
  作者：Hiroyuki Ishibashi、Nahoko Uemura、Hiroshi Nakatani、Mika Okazaki、Tatsunori Sato、Nobuyuki Nakamura、Masazumi Ikeda

  DOI：10.1021/jo00061a005

  日期：1993.4

  A new method for the synthesis of five-membered lactams by ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic alpha-chloro-alpha-thioacetamides and the application of the method to the synthesis of the title alkaloids are described. A benzene solution of N-allyl-N-methyl-alpha-chloro-alpha-(phenylthio)acetamide (6) was heated at 140-degrees-C in the presence of RuCl2(PPh3)3 to give alpha-thio-beta-(chloromethyl)-substituted gamma-lactam 8 as a mixture of cis and trans isomers in a ratio of ca. 3:7. NH congener 11, however, gave no cyclization product. Heating chloro sulfides 18 and 19, prepared from L-prolinol, with RuCl2(PPh3)3 afforded bicyclic lactams 20 and 21, respectively. Treatment of 20 with cesium propanoate gave predominantly cyclopropane derivative 25, whereas S-methyl congener 21 provided esters 24 in good yield. Desulfurization of 24 with Raney nickel followed by reduction with LiAlH4 furnished (-)-trachelanthamidine (28). On the other hand, N-(cyclohex-2-en-1-yl) derivative 30, when heated with RuCl2(PPh3)3, afforded octahydroindol-2-ones 31a,b. The formation of 31a,b indicated that the intramolecular addition of the chloro sulfide of 30 to the olefinic bond proceeded in an anti-mode. By contrast, 2-phenyl-substituted derivative 38 gave syn-addition product 39. The difference between the modes of cyclization of 30 and 38 can be explained by assuming the intermediacy of radical 34. When R = H, the chlorine atom attacks the convex face of the fused bicyclic system of 34 to lead to 31a,b, whereas the steric bulk of the angular phenyl group (R = Ph) is apparently sufficient to direct the chlorine atom to the concave face. Heating chloro sulfide 48, prepared in a highly stereocontrolled manner from cyclohexene 42, with RuCl2(PPh3)3 afforded bicyclic lactam 49. Oxidation of 49 with m-CPBA followed by Pummerer rearrangement/hydrolysis gave keto lactam 51, which was dehydrochlorinated with DBU to give olefin 52. LiAlH4 reduction of 52 and acylation with pivaloyl chloride provided ester 54, a key intermediate in Martin's total synthesis of (+/-)-haemanthidine (41) and (+/-)-pretazettine (40).
• Fluorination of sulfanyl amides using difluoroiodoarene reagents
  作者：William B. Motherwell、Michael F. Greaney、Jeremy J. Edmunds、Jonathan W. Steed

  DOI：10.1039/b209078c

  日期：2002.12.19

  A range of sulfur-containing amides have been fluorinated with the hypervalent iodine difluoride reagents 1, and two principal reaction pathways identified. Cephalosporin esters 2 having a heteroatom in the α-position to sulfur undergo fluorination in DCM with cleavage of the carbon–sulfur bond to form novel fluorinated β-lactams 4. Sulfides with electron-withdrawing groups in the α-position undergo α-fluorination in a process analogous to the classical Pummerer reaction. This Fluoro-Pummerer reaction has been exemplified for a range of simple α-phenylsulfanylacetamides 14–19. When β-hydrogens are present in the substrate a different route is followed, with deprotonation by basic fluoride taking place to yield vinyl sulfides 41–43. When an excess of the fluorinating reagent is used these vinyl sulfides can undergo further reaction in a novel tandem Pummerer-Additive-Pummerer process to yield α,β-difluoro sulfides 45–47.

  使用高价二氟化碘试剂 1 对一系列含硫酰胺进行了氟化处理，并确定了两种主要的反应途径。头孢菌素酯 2 在硫的α位上有一个杂原子，在二氯甲烷中发生氟化反应，碳-硫键断裂，形成新型氟化β-内酰胺 4。在 α 位上带有抽电子基团的硫化物在类似于经典普默尔反应的过程中发生 α-氟化反应。这种氟-普默尔反应已在一系列简单的 α-苯硫基乙酰胺 14-19 中得到验证。当底物中含有 β 氢时，则采用不同的途径，通过碱性氟化物进行去质子化反应，生成乙烯基硫化物 41-43。当使用过量的氟化试剂时，这些乙烯基硫化物可在新型串联式普默尔-添加剂-普默尔工艺中发生进一步反应，生成 α,β-二氟硫化物 45-47。