rac-N-(cyclohex-2-enyl)-2-iodo-4,6-dimethylaniline | 1240966-20-4

• 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: rac-N-(cyclohex-2-enyl)-2-iodo-4,6-dimethylaniline
• 英文别名: N-(cyclohex-2-enyl)-2-iodo-4,6-dimethylaniline
• CAS: 1240966-20-4
• 化学式: C₁₄H₁₈IN
• 分子量: 327.208
• InChiKey: UELXOEJHHGAZMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  rac-N-(cyclohex-2-enyl)-2-iodo-4,6-dimethylaniline 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 potassium carbonate 、 三乙胺 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 144.0h， 生成 rac-(E)-t-butyl 3-(2-(N-(cyclohex-2-enyl)acetamido)-3,5-dimethylphenyl)acrylate
  参考文献：
  名称：

  Radical and Heck Cyclizations of Diastereomeric o-Haloanilide Atropisomers

  摘要：

  The outcomes of radical cyclizations and Heck reactions of N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamides depend critically on the configurations of the chiral axis and the stereocenter. In substrates without an or-rho-methyl group, the diastereomeric precursors interconvert slowly at ambient temperatures. Cyclization of enriched mixtures of diastereomers provided similar yields of acetyl tetrahydrocarbazoles or dihydrocarbazoles, suggesting that interconversion of the radical or organometallic intermediates also occurs. Diastereomers of N-(cyclohex-2-enyl)-N-(2-iodo-4,6-dimethylphenyl)acetamides with an additional ortnomethyl group did not interconvert at ambient temperatures and were readily resolved. In radical cyclizations, syn diastereomers were prone to cyclize, while anti isomers were not. Strikingly, Heck reactions gave the opposite result; anti isomers were prone to cyclization and syn isomers were not. Heck reactions of allylic acetates occur with beta-hydride elimination when acetate is trans to palladium and with beta-acetoxy elimination when acetate is cis. This is surprising because prior studies have suggested that a trans relationship of palladium and acetoxy is essential for acetate elimination. Analyses of the results provide insights into mechanisms for radical cyclization and for insertion and elimination in the Heck reaction.

  DOI：

  10.1021/ja108795x
• 作为产物：
  描述：

  2-碘-4,6-二甲基苯胺 、 3-溴环己烯 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 18.17h， 以61%的产率得到rac-N-(cyclohex-2-enyl)-2-iodo-4,6-dimethylaniline
  参考文献：
  名称：

  Radical and Heck Cyclizations of Diastereomeric o-Haloanilide Atropisomers

  摘要：

  The outcomes of radical cyclizations and Heck reactions of N-(cyclohex-2-enyl)-N-(2-iodophenyl)acetamides depend critically on the configurations of the chiral axis and the stereocenter. In substrates without an or-rho-methyl group, the diastereomeric precursors interconvert slowly at ambient temperatures. Cyclization of enriched mixtures of diastereomers provided similar yields of acetyl tetrahydrocarbazoles or dihydrocarbazoles, suggesting that interconversion of the radical or organometallic intermediates also occurs. Diastereomers of N-(cyclohex-2-enyl)-N-(2-iodo-4,6-dimethylphenyl)acetamides with an additional ortnomethyl group did not interconvert at ambient temperatures and were readily resolved. In radical cyclizations, syn diastereomers were prone to cyclize, while anti isomers were not. Strikingly, Heck reactions gave the opposite result; anti isomers were prone to cyclization and syn isomers were not. Heck reactions of allylic acetates occur with beta-hydride elimination when acetate is trans to palladium and with beta-acetoxy elimination when acetate is cis. This is surprising because prior studies have suggested that a trans relationship of palladium and acetoxy is essential for acetate elimination. Analyses of the results provide insights into mechanisms for radical cyclization and for insertion and elimination in the Heck reaction.

  DOI：

  10.1021/ja108795x

文献信息

• Memory of Axial Chirality in Aryl Radical Phosphanylations
  作者：Achim Bruch、Andrea Ambrosius、Roland Fröhlich、Armido Studer、David B. Guthrie、Hanmo Zhang、Dennis P. Curran

  DOI：10.1021/ja105070k

  日期：2010.8.25

  The rate constant for phosphanylation of an aryl radical with trimethylstannyl diphenylphosphane (Me(3)SnPPh(2)) has been measured as k(phos) approximate to 9 x 10(8) M(-1) s(-1). Aryl radicals derived from several axially chiral o-haloanilides are trapped by Me(3)SnPPh(2) with complete retention of axial chirality as shown by oxidation of the phosphanes to give stable, easily analyzed phosphane oxides or sulfides. Double phosphanylations of o,o'-dihaloanilides followed by treatment with H(2)O(2) or S(8) in either order give enantiomers of a mixed diphosphane oxide sulfide. Chemodivergent trapping of diastereomers of an N-(cyclohex-2-enyl)anilide anilide is observed. For one isomer, the cyclization precedes the Me(3)SnPPh(2) trapping, while for the other isomer direct trapping with Me(3)SnPPh(2) supersedes the cyclization. The products are chiral triaryl phosphanes, oxides, and sulfides that are potentially interesting ligands in asymmetric catalysis.