N-(5R-methylcyclohex-2-en-1-ylidene)-4-methylbenzenesulfonamide | 1610853-59-2

• 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: N-(5R-methylcyclohex-2-en-1-ylidene)-4-methylbenzenesulfonamide
• 英文别名: 4-methyl-N-[(5R)-5-methylcyclohex-2-en-1-ylidene]benzenesulfonamide
• CAS: 1610853-59-2
• 化学式: C₁₄H₁₇NO₂S
• 分子量: 263.36
• InChiKey: AKAWFZBKAPYLTK-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  54.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(5R-methylcyclohex-2-en-1-ylidene)-4-methylbenzenesulfonamide 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 甲酸 、 [(1S,2S)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium (I) 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 三乙胺 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 20.75h， 生成 N-[(1S,3R,5S)-3-methyl-5-phenylcyclohexyl]-4-methylbenzenesulfonamide
  参考文献：
  名称：

  铑催化的1,4-加成反应及随后的立体发散还原反应，对映选择性地制备3-芳基环烷基胺

  摘要：

  AbstractN‐Sulfonylimines of cycloalk‐2‐enones are well‐suited for the enantioselective rhodium(I)/binap‐catalyzed 1,4‐additions of arylzinc halides. The cyclic enamides, obtained after quenching, are sensitive towards chromatography, but can undergo diastereoselective reductions to furnish cis‐ or trans‐3‐arylcycloalkylamines with five‐ to seven‐membered rings. The 1,4‐addition is not influenced by a methyl group at C‐5 of six‐membered rings, providing further configurational options. 3‐Arylcycloalkylamines are subunits in a number of bioactive substances and can also be oxidatively transformed into cyclic γ‐amino acids.magnified image

  DOI：

  10.1002/adsc.201400824

文献信息

• Copper-catalyzed enantioselective 1,4-addition of alkyl groups to N-sulfonyl imines
  作者：Johannes Westmeier、Paultheo von Zezschwitz

  DOI：10.1039/c4cc07134d

  日期：——

  In copper(I)/phosphoramidite-catalyzed asymmetric 1,4-additions of dialkylzinc, N-sulfonyl imines are more reactive and furnish higher enantiomeric excesses than the respective cycloalk-2-enones. This enables formation of a quaternary stereocenter as well as a cis-selective addition to an imine derived from 5-methylcyclohex-2-enone. The 1,4-adducts can be transformed in stereodivergent reductions yielding cis- or trans-3-alkylcycloalkyl amides.

  在铜(I)/膦酰胺催化下，二烷基锌对N-磺酰基亚胺的1,4-加成反应比对应的环烷-2-烯酮更具活性，并且能获得更高的对映体过剩。这使得能够形成一个季碳立体中心，以及对源自5-甲基环己-2-烯酮的亚胺进行顺式选择性加成。这些1,4-加成产物可以通过立体发散性还原反应转化为顺式或反式的3-烷基环烷基酰胺。
• Rhodium-Catalyzed Enantioselective Addition of Organoaluminum Reagents to<i>N</i>-Tosyl Ketimines
  作者：Sebastian Hirner、Andreas Kolb、Johannes Westmeier、Sandra Gebhardt、Stephen Middel、Klaus Harms、Paultheo von Zezschwitz

  DOI：10.1021/ol501372u

  日期：2014.6.6

  Rhodium(I)/Binap complexes catalyze highly enantioselective additions of methyl- and arylaluminum reagents to cyclic α,β-unsaturated N-tosyl ketimines. Depending on the solvent and substituents at the ring, the reaction occurs either in a 1,2-manner to deliver α-tertiary allylic amines or in a 1,4-manner to yield, after subsequent reduction, 3-substituted cycloalkyl amines. Well known in the case of

  铑（I）/ Binap络合物催化甲基和芳基铝试剂向环状α，β-不饱和N-甲苯磺酰基酮亚胺的高度对映选择性加成。取决于环上的溶剂和取代基，该反应以1，2-方式发生以递送α-叔烯丙基胺，或者以1，4-方式发生，以在随后的还原之后产生3-取代的环烷基胺。在各个环烯酮的情况下众所周知，氮杂类似物的这些第一转化使得能够合成具有药物和生化意义的胺结构。
• Enantioselective Preparation of 3-Arylcycloalkylamines by Rhodium-Catalyzed 1,4-Addition and Subsequent Stereodivergent Reduction
  作者：Sandra Gebhardt、Christian H. Müller、Johannes Westmeier、Klaus Harms、Paultheo von Zezschwitz

  DOI：10.1002/adsc.201400824

  日期：2015.2.9

  AbstractN‐Sulfonylimines of cycloalk‐2‐enones are well‐suited for the enantioselective rhodium(I)/binap‐catalyzed 1,4‐additions of arylzinc halides. The cyclic enamides, obtained after quenching, are sensitive towards chromatography, but can undergo diastereoselective reductions to furnish cis‐ or trans‐3‐arylcycloalkylamines with five‐ to seven‐membered rings. The 1,4‐addition is not influenced by a methyl group at C‐5 of six‐membered rings, providing further configurational options. 3‐Arylcycloalkylamines are subunits in a number of bioactive substances and can also be oxidatively transformed into cyclic γ‐amino acids.magnified image