1-cyclohexyl-N-diphenylphosphoryl-1-(4-methylphenyl)sulfonylmethanamine | 701291-89-6

• 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: 1-cyclohexyl-N-diphenylphosphoryl-1-(4-methylphenyl)sulfonylmethanamine
• CAS: 701291-89-6
• 化学式: C₂₆H₃₀NO₃PS
• 分子量: 467.569
• InChiKey: TYPKVMYBHGPSSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  71.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-cyclohexyl-N-diphenylphosphoryl-1-(4-methylphenyl)sulfonylmethanamine 在 碳酸氢钠 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 生成 N-cyclohexylmethylenediphenylphosphinamide
  参考文献：
  名称：

  NHC–Cu-Catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-Substituted Homoallenylamides and Application to the Synthesis of S-(−)-Cyclooroidin

  摘要：

  A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(-)-cyclooroidin.

  DOI：

  10.1021/ja500373s
• 作为产物：
  描述：

  对甲苯亚磺酸 、 二苯基磷酰胺 、 环己烷基甲醛 生成 1-cyclohexyl-N-diphenylphosphoryl-1-(4-methylphenyl)sulfonylmethanamine
  参考文献：
  名称：

  Design and synthesis of a tridentate ligand inspired by the phenomenon of self-assembly catalysis and its application in the asymmetric alkynylation of N-(diphenylphosphinoyl) imines

  摘要：

  On the basis of the phenomenon of self-assembly catalysis, a tridentate ligand was designed and synthesized in two steps. The application in alkynylation of N-(diphenylphosphinoyl) imines gave the expected products. Aromatic, heteroaromatic N-(diphenylphosphinoyl) imines were employed and gave optically active propargylic amines in good yields (up to 89%) and excellent enantioselectivities (up to 96%) by a simple experimental procedure. The direct use of sulfone amides in the alkynylation of N-(diphenylphosphinoyl) aliphatic imines made this method very attractive. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.07.020

文献信息

• Organocatalytic trifluoromethylation of imines using phase-transfer catalysis with phenoxides. A general platform for catalytic additions of organosilanes to imines
  作者：Luca Bernardi、Eugenio Indrigo、Salvatore Pollicino、Alfredo Ricci

  DOI：10.1039/c0cc05777k

  日期：——

  A new approach to additions of silicon nucleophiles to imines was developed. The method is based on the phase-transfer of phenoxides by ammonium catalysts, overcoming the inability of amide adducts in promoting the reactions.

  一种新的硅亲核试剂与亚胺加成的方法被开发出来。该方法基于铵催化剂对酚氧化物的相转移，克服了酰胺加成物促进反应的局限性。
• A Direct Catalytic Asymmetric Mannich-type Reaction via a Dinuclear Zinc Catalyst:  Synthesis of Either <i>anti</i>- or <i>s</i><i>yn</i>-α-Hydroxy-<i>β</i>-Amino Ketones
  作者：Barry M. Trost、Jaray Jaratjaroonphong、Vichai Reutrakul

  DOI：10.1021/ja057498v

  日期：2006.3.1

  The use of imines bearing a hydrolyzable nitrogen substituent in direct asymmetric Mannich reactions with α-hydroxyketones is developed. Previous work focused on the use of N-arylimines or nonenolizable imines, and the latter with only methoxy-substituted α-hydroxyacetophenones. Using a dinuclear catalyst devised from 2,6-di-(S)-2‘-diphenylhydroxymethylpyrrolidino-N-methyl)-4-methylphenol and diethylzinc

  开发了带有可水解氮取代基的亚胺在与 α-羟基酮的直接不对称曼尼希反应中的应用。以前的工作集中在使用 N-芳基亚胺或非烯醇化亚胺，后者仅使用甲氧基取代的 α-羟基苯乙酮。使用由 2,6-二-(S)-2'-二苯基羟甲基吡咯烷-N-甲基)-4-甲基苯酚和二乙基锌设计的双核催化剂，广泛的羟基乙酰化芳烃，包括苯基、2-呋喃基、1-萘基、与2-萘基反应良好。此外，反应集中在使用烯醇化亚胺。对于 N-二苯基膦酰基，除了 2-甲氧基-2'-羟基乙酰苯的反应外，该反应具有抗选择性，对映体过量范围为 83% 至 99%。使用 N-Boc-亚胺，该反应是顺式选择性的，对映体过量为 90% 至 94%。非对映选择性对 N-取代基性质的依赖性可能源于二苯基膦酰基的空间需求。
• Direct catalytic asymmetric Mannich-type reactions of isomerizable aliphatic imines: chemoselective enolate formation from a hydroxyketone by a Zn-catalyst
  作者：Akitake Yamaguchi、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1016/j.tetlet.2006.04.016

  日期：2006.6

  A direct catalytic asymmetric Mannich-type reaction of isomerizable aliphatic imines is described. A Et2Zn/(S,S)-linked-BINOL complex was suitable for chemoselective enolate formation from a hydroxyketone in the presence of isomerizable aliphatic N-diphenylphosphinoyl imines. The reaction proceeds smoothly and β-alkyl-β-amino-α-hydroxyketones were obtained in good yield and high enantioselectivity

  描述了可异构化的脂族亚胺的直接催化不对称曼尼希型反应。在可异构化的脂族N-二苯基膦酰基亚胺的存在下，Et 2 Zn /（S，S）-连接的BINOL络合物适合于由羟基酮形成化学选择性烯醇盐。反应进行得很顺利，尽管具有中等至低非对映选择性，但仍能以良好的收率和高对映选择性（高达99％ee）获得β-烷基-β-氨基-α-羟基酮。
• Trichloromethyl Ketones as Synthetically Versatile Donors: Application in Direct Catalytic Mannich-Type Reactions and the Stereoselective Synthesis of Azetidines
  作者：Hiroyuki Morimoto、Sean H. Wiedemann、Akitake Yamaguchi、Shinji Harada、Zhihua Chen、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1002/anie.200600227

  日期：2006.5.5
• Design and synthesis of a tridentate ligand inspired by the phenomenon of self-assembly catalysis and its application in the asymmetric alkynylation of N-(diphenylphosphinoyl) imines
  作者：Wenjin Yan、Peng Li、Jingchao Feng、Dong Wang、Shaoqun Zhu、Xianxing Jiang、Rui Wang

  DOI：10.1016/j.tetasy.2010.07.020

  日期：2010.8

  On the basis of the phenomenon of self-assembly catalysis, a tridentate ligand was designed and synthesized in two steps. The application in alkynylation of N-(diphenylphosphinoyl) imines gave the expected products. Aromatic, heteroaromatic N-(diphenylphosphinoyl) imines were employed and gave optically active propargylic amines in good yields (up to 89%) and excellent enantioselectivities (up to 96%) by a simple experimental procedure. The direct use of sulfone amides in the alkynylation of N-(diphenylphosphinoyl) aliphatic imines made this method very attractive. (C) 2010 Elsevier Ltd. All rights reserved.