dimethyl (R)-hydroxy(p-chlorophenyl)methylphosphonate

• 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: dimethyl (R)-hydroxy(p-chlorophenyl)methylphosphonate
• 英文别名: dimethyl (R)-hydroxy(4-chlorophenyl)methylphosphonate；dimethyl [hydroxy(4-chlorophenyl)methyl]phosphonate；(R)-dimethyl ((4-chlorophenyl)(hydroxy)methyl)phosphonate；(R)-(4-chlorophenyl)-dimethoxyphosphorylmethanol
• 化学式: C₉H₁₂ClO₄P
• 分子量: 250.619
• InChiKey: XWQYSORCBYSVKR-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-氯苯甲醛 、 亚磷酸二甲酯 在 C₃₈H₄₈N₄P⁽¹⁺⁾*Cl^(1-) 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 5.5h， 以99%的产率得到dimethyl (R)-hydroxy(p-chlorophenyl)methylphosphonate
  参考文献：
  名称：

  [5.5]-P-螺环手性三氨基亚氨基正膦催化醛和炔酮的不对称氢膦酰化

  摘要：

  描述了由 [5.5]-P-螺环手性三氨基亚氨基正膦作为碱催化剂介导的醛和炔酮的高效和对映选择性氢膦酰化的开发。天...

  DOI：

  10.1246/bcsj.20170040

文献信息

• Synthesis of an Optically Active Al(salalen) Complex and Its Application to Catalytic Hydrophosphonylation of Aldehydes and Aldimines
  作者：Bunnai Saito、Hiromichi Egami、Tsutomu Katsuki

  DOI：10.1021/ja0651005

  日期：2007.2.1

  serve as an efficient catalyst for hydrophosphonylation of aldehydes and aldimines, giving the corresponding alpha-hydroxy and alpha-amino phosphonates with high enantioselectivity, respectively. The scope of the hydrophosphonylation was wide, and both aliphatic and aromatic aldehydes and aldimines were successfully used as substrates for the reaction. The potent catalysis of the complex is attributed to

  以模块化合成方式新合成了光学活性铝（salalen）配合物2，发现它可作为醛和醛亚胺氢膦酰化的有效催化剂，分别得到相应的具有高对映选择性的α-羟基和α-氨基膦酸酯. 氢膦酰化的范围很广，脂肪族和芳香族醛和醛亚胺都成功地用作反应的底物。该复合物的强大催化作用归因于其独特的结构：它采用扭曲的三角双锥体构型，这使得 salalen 配体呈顺式-β 样结构，其中手性氨基位于靠近金属中心的位置。
• Enantioselective Hydrophosphonylation of Aldehydes Using an Aluminum Binaphthyl Schiff Base Complex as a Catalyst
  作者：Katsuji Ito、Hironori Tsutsumi、Masayuki Setoyama、Bunnai Saito、Tsutomu Katsuki

  DOI：10.1055/s-2007-984528

  日期：2007.7

  An aluminum binaphthyl Schiff base complex was found to be an efficient catalyst for enantioselective hydrophosphonylation of aldehydes. High enantioselectivities were obtained in reactions of both aromatic and aliphatic aldehydes (up to 84% and 86% ee, respectively).

  研究发现，一种铝二萘基希夫碱复合物是对映体选择性氢膦酰化醛的高效催化剂。在芳香醛和脂肪醛的反应中都获得了较高的对映选择性（ee值分别高达 84% 和 86%）。
• Asymmetric hydrogenation of α-keto phosphonates with chiral phosphine–phosphoramidite ligands
  作者：Qing Li、Chuan-Jin Hou、Yan-Jun Liu、Rui-Feng Yang、Xiang-Ping Hu

  DOI：10.1016/j.tetasy.2015.05.007

  日期：2015.7

  Rh-catalyzed asymmetric hydrogenation of challenging α-keto phosphonates has been developed. With a new chiral phosphine–phosphoramidite ligand, a wide range of α-keto phosphonates were hydrogenated to afford the corresponding (R)-α-hydroxy phosphonates with moderate to good enantioselectivities (up to 87% ee).

  已经开发出具有挑战性的α-酮膦酸酯的Rh催化不对称氢化。使用新的手性膦-亚磷酰胺配体，可将多种α-酮膦酸酯氢化，得到相应的（R）-α-羟基膦酸酯，具有中等至良好的对映选择性（最高87％ee）。
• Enantioselective synthesis of α-hydroxy phosphonates via oxidation with (camphorsulfonyl)oxaziridines
  作者：Diana M. Pogatchnik、David F. Wiemer

  DOI：10.1016/s0040-4039(97)00705-3

  日期：1997.5

  Reaction of phosphonate anions with enantiomerically pure (camphorsulfonyl)oxaziridines results in formation of nonracemic alpha-hydroxy phosphonates. This enantioselective hydroxylation methodology provides convenient access to optically active alpha-hydroxy phosphonates and their corresponding phosphonic acids. (C) 1997 Elsevier Science Ltd.
• Catalytic Asymmetric Synthesis of α-Hydroxy Phosphonates Using the Al−Li−BINOL Complex
  作者：Takayoshi Arai、Masahiro Bougauchi、Hiroaki Sasai、Masakatsu Shibasaki

  DOI：10.1021/jo960180o

  日期：1996.1.1