(R)-N-((4-chlorophenyl)(4-methoxyphenyl)methyl)-4-methylbenzenesulfonamide | 796966-23-9

• 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: (R)-N-((4-chlorophenyl)(4-methoxyphenyl)methyl)-4-methylbenzenesulfonamide
• 英文别名: N-[(R)-(4-chlorophenyl)-(4-methoxyphenyl)methyl]-4-methylbenzenesulfonamide
• CAS: 796966-23-9
• 化学式: C₂₁H₂₀ClNO₃S
• 分子量: 401.914
• InChiKey: UKKLUUJFLWKXAS-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  63.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲苯磺酰胺 在 三氟化硼乙醚 、 di-μ-chloro-bis[(η⁵-(4`R,5`R)-(Sp)-2-(2`-4`,5`-dihydro-4`,5`-diphenyl-1`-tosyl-1`H-imidazolyl)cyclopentadienyl,1-C,3`-N)(η⁵-cyclopentadienyl)-iron(II)]dipalladium(II) 、 silver(I) acetate 作用下， 以 氯苯 、 甲苯 为溶剂， 反应 20.0h， 生成 (R)-N-((4-chlorophenyl)(4-methoxyphenyl)methyl)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  高度对映选择性的二茂铁基戊四环乙酸-乙酸酯催化亚胺和酮亚胺与芳基硼氧烷的芳基化

  摘要：

  苯甲酰N取代的立体中心构成药物中的常见结构基序。因此，它们的高度对映选择性的产生具有技术重要性。一种有吸引力的策略是亚胺与有机硼试剂的芳基化。对于这种反应类型，手性Rh配合物已经达到很高的生产率。在本文中，我们描述了富电子的Pd II与最佳的Rh催化剂相比，该催化剂在醛亚胺的芳基化中也表现出色。二茂铁戊四环乙酸酯催化剂可实现较宽的底物范围和极高的对映选择性。常见的副反应如芳基-芳基均偶联和亚胺水解可被阻止。机理研究表明，a）乙酸盐配体对于金属转移至关重要，b）活性催化剂很可能是保拉达环-OAc单体，c）限速步骤可能是产物释放。通过添加KOAc，芳基化反应也可以应用于酮亚胺。

  DOI：

  10.1002/chem.201605244

文献信息

• Exogenous-Base-Free Palladacycle-Catalyzed Highly Enantioselective Arylation of Imines with Arylboroxines
  作者：Carmen Schrapel、René Peters

  DOI：10.1002/anie.201501846

  日期：2015.8.24

  Enantiomerically pure benzylic amines are important for the development of new drugs. A readily accessible planar‐chiral ferrocene‐derived palladacycle is shown to be a highly efficient catalyst for the formation of N‐substituted benzylic stereocenters; this catalyst accelerates the 1,2‐addition of arylboroxines to aromatic and aliphatic imines with exceptional levels of enantioselectivity. Using aldimines

  对映体纯的苄基胺对于新药的开发很重要。易于获得的平面手性二茂铁衍生的palladacycle被证明是形成N取代的苄基立体中心的高效催化剂。这种催化剂以极高的对映选择性加速芳基硼氧烷与芳族和脂族亚胺的1,2-加成反应。当乙酸盐用作阴离子配体时，使用醛亚胺对硼氧烷的活化不是必需的外源性碱。常见的问题（如芳基-芳基均偶联和亚胺水解）已被完全克服，后者即使在没有分子筛的情况下也是如此。
• Design and synthesis of new chiral phosphorus–olefin bidentate ligands and their use in the rhodium-catalyzed asymmetric addition of organoboroxines to N-sulfonyl imines
  作者：Ryo Shintani、Rintaro Narui、Yosuke Tsutsumi、Sayuri Hayashi、Tamio Hayashi

  DOI：10.1039/c1cc11823d

  日期：——

  Novel chiral phosphorus-olefin bidentate ligands have been synthesized in a few steps from a readily available enantiopure compound. These ligands have been applied to a rhodium-catalyzed asymmetric addition of organoboroxines to N-sulfonyl aldimines, achieving high yield and enantioselectivity.

  新型的手性磷-烯烃双齿配体已由易于获得的对映纯化合物经数步合成。这些配体已被用于铑催化的将有机硼氧烷酮不对称加成到N-磺酰基醛亚胺上，从而实现了高收率和对映选择性。
• <i>C</i>₂-Symmetric Bicyclo[2.2.2]octadienes as Chiral Ligands:  Their High Performance in Rhodium-Catalyzed Asymmetric Arylation of <i>N</i>-Tosylarylimines
  作者：Norihito Tokunaga、Yusuke Otomaru、Kazuhiro Okamoto、Kazuhito Ueyama、Ryo Shintani、Tamio Hayashi

  DOI：10.1021/ja044790e

  日期：2004.10.1

  Asymmetric synthesis of diarylmethylamines with high enantioselectivity (95-99% ee) was realized by use of a new C2-symmetric diene ligand, (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene (Ph-bod*), for the rhodium-catalyzed asymmetric arylation of N-tosylarylimines with arylboroxines.
• <i>C</i>₁-Symmetric Dicyclopentadienes as New Chiral Diene Ligands for Asymmetric Rhodium-Catalyzed Arylation of <i>N</i>-Tosylarylimines
  作者：Cheng Shao、Hong-Jie Yu、Nuo-Yi Wu、Chen-Guo Feng、Guo-Qiang Lin

  DOI：10.1021/ol101531r

  日期：2010.9.3

  Monosubstituted Crsymmetric dicyclopentadienes as a new class of diene ligands have been developed for asymmetric arylation of N-tosylarylimines in excellent yields (98-99%) with high enantioselectivities (90-96%). The preparation of these diene ligands relied on an efficient lipase-catalyzed resolution as the key step.
• Design of <i>C</i><i>₂</i>-Symmetric Tetrahydropentalenes as New Chiral Diene Ligands for Highly Enantioselective Rh-Catalyzed Arylation of <i>N</i>-Tosylarylimines with Arylboronic Acids
  作者：Zhi-Qian Wang、Chen-Guo Feng、Ming-Hua Xu、Guo-Qiang Lin

  DOI：10.1021/ja0710914

  日期：2007.5.1

  A new type of C-2-symmetric chiral diene ligand bearing a simple bicyclic [3.3.0] backbone was discovered. (3aS,6aS)-3,6-diphenyl-1,3a,4,6a-tetrahydropentalene was applied successfully in the Rh-catalyzed asymmetric arylation of N-tosylarylimines with arylboronic acids. With the new chiral diene ligand, a broad range of highly enantiomerically enriched diarylmethylamines (98-99% ee) as well as 3-aryl substituted phthalimidines (99% ee) could be easily prepared.