1-(4,5-dimethoxy-2-(methylthio)phenyl)nonan-1-one | 1359978-91-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(4,5-dimethoxy-2-(methylthio)phenyl)nonan-1-one
• 英文别名: 1-(4,5-Dimethoxy-2-methylsulfanylphenyl)nonan-1-one；1-(4,5-dimethoxy-2-methylsulfanylphenyl)nonan-1-one
• CAS: 1359978-91-8
• 化学式: C₁₈H₂₈O₃S
• 分子量: 324.485
• InChiKey: JNQIDQKGOLRYHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  22
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(4,5-dimethoxy-2-(methylthio)phenyl)nonan-1-one 在 三乙氧基硅烷 作用下， 以 1,2-二氯乙烷 为溶剂， 以35 mg的产率得到1-(3,4-dimethoxyphenyl)nonan-1-one
  参考文献：
  名称：

  无痕螯合控制的铑催化的分子间烯烃和炔烃加氢酰化反应

  摘要：

  一种新的能够耐受铑的催化，硫化物还原的功能基团，与铑催化的螯合控制的加氢酰化反应相结合，形成了无痕的加氢酰化方案。芳基和烯基醛可与烯烃，炔烃和丙二烯结合使用，以高收率得到无痕产物。还提出了初步的机械建议。

  DOI：

  10.1002/chem.201204056
• 作为产物：
  描述：

  1-辛炔 、 4,5-dimethoxy-2-(methylthio)benzaldehyde 在 bis(norbornadiene)rhodium(l)tetrafluoroborate 、 氢气 、 双(二环己基膦)甲烷 作用下， 以 丙酮 为溶剂， 反应 3.0h， 以80%的产率得到1-(4,5-dimethoxy-2-(methylthio)phenyl)nonan-1-one
  参考文献：
  名称：

  Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne Carbothiolation: Arene Functionalization with Activating Group Recycling

  摘要：

  A Rh(I)-catalyzed method for the efficient functionalization of arenes is reported. Aryl methyl sulfides are combined with terminal alkynes to deliver products of carbothiolation. The overall process results in reincorporation of the original arene functional group, a methyl sulfide, into the products as an alkenyl sulfide. The carbothiolation process can be combined with an initial Rh(I)-catalyzed alkene or alkyne hydroacylation reaction in three-component cascade sequences. The utility of the alkenyl sulfide products is also demonstrated in simple carbo- and heterocycle-forming processes. We also provide mechanistic evidence for the course of this new process.

  DOI：

  10.1021/ja2108992

文献信息

• Intermolecular Hydroacylation: High Activity Rhodium Catalysts Containing Small-Bite-Angle Diphosphine Ligands
  作者：Adrian B. Chaplin、Joel F. Hooper、Andrew S. Weller、Michael C. Willis

  DOI：10.1021/ja211649a

  日期：2012.3.14

  rhodium complexes containing methylene bridged diphosphine ligands, viz. [Rh(C(6)H(5)F)(R(2)PCH(2)PR'(2))][BAr(F)(4)] (R, R' = (t)Bu or Cy; Ar(F) = C(6)H(3)-3,5-(CF(3))(2)), are shown to be practical and very efficient precatalysts for the intermolecular hydroacylation of a wide variety of unactivated alkenes and alkynes with β-S-substituted aldehydes. Intermediate acyl hydride complexes [Rh((t)Bu(2)PCH

  含有亚甲基桥联二膦配体的易于制备且可长期稳定的铑配合物，即。[Rh(C(6)H(5)F)(R(2)PCH(2)PR'(2))][BAr(F)(4)] (R, R' = (t)Bu 或 Cy ; Ar(F) = C(6)H(3)-3,5-(CF(3))(2))，被证明是一种实用且非常有效的预催化剂，可用于多种未活化烯烃的分子间加氢酰化和带有 β-S-取代醛的炔烃。中间酰基氢化物复合物 [Rh((t)Bu(2)PCH(2)P(t)Bu(2))Hκ(2)(S,C)-SMe(C(6)H(4)CO )}(L)](+)（L = 丙酮、MeCN、[NCCH(2)BF(3)](-)）和脱羰产物 [Rh((t)Bu(2)PCH(2)P( t)Bu(2))(CO)(SMePh)](+) 已在溶液中并通过 X 射线晶体学从使用 2-(甲硫基) 苯甲醛的化学计量反应中表征。还报道了与膦 2-(二苯基膦基)苯甲醛
• Activating Group Recycling in Action: A Rhodium-Catalyzed Carbothiolation Route to Substituted Isoquinolines
  作者：Milan Arambasic、Joel F. Hooper、Michael C. Willis

  DOI：10.1021/ol402650q

  日期：2013.10.18

  A new rhodium(l) catalyst allows practical and efficient alkyne carbothiolation reactions to be achieved on synthetically useful ketone-bearing aryl methyl sulfides. The carbothiolation adducts, featuring a 'recycled methyl sulfide' activating group, are convenient precursors to highly substituted isoquinolines.
• Traceless Chelation-Controlled Rhodium-Catalyzed Intermolecular Alkene and Alkyne Hydroacylation
  作者：Joel F. Hooper、Rowan D. Young、Andrew S. Weller、Michael C. Willis

  DOI：10.1002/chem.201204056

  日期：2013.2.25

  A new functional‐group tolerant, rhodium‐catalyzed, sulfide‐reduction process is combined with rhodium‐catalyzed chelation‐controlled hydroacylation reactions to give a traceless hydroacylation protocol. Aryl‐ and alkenyl aldehydes can be combined with both alkenes, alkynes and allenes to give traceless products in high yields. A preliminary mechanistic proposal is also presented.

  一种新的能够耐受铑的催化，硫化物还原的功能基团，与铑催化的螯合控制的加氢酰化反应相结合，形成了无痕的加氢酰化方案。芳基和烯基醛可与烯烃，炔烃和丙二烯结合使用，以高收率得到无痕产物。还提出了初步的机械建议。
• Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne Carbothiolation: Arene Functionalization with Activating Group Recycling
  作者：Joel F. Hooper、Adrian B. Chaplin、Carlos González-Rodríguez、Amber L. Thompson、Andrew S. Weller、Michael C. Willis

  DOI：10.1021/ja2108992

  日期：2012.2.15

  A Rh(I)-catalyzed method for the efficient functionalization of arenes is reported. Aryl methyl sulfides are combined with terminal alkynes to deliver products of carbothiolation. The overall process results in reincorporation of the original arene functional group, a methyl sulfide, into the products as an alkenyl sulfide. The carbothiolation process can be combined with an initial Rh(I)-catalyzed alkene or alkyne hydroacylation reaction in three-component cascade sequences. The utility of the alkenyl sulfide products is also demonstrated in simple carbo- and heterocycle-forming processes. We also provide mechanistic evidence for the course of this new process.