(S)-dibenzyl [hydroxy(phenyl)methyl]phosphonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (S)-dibenzyl [hydroxy(phenyl)methyl]phosphonate
• 英文别名: dibenzyl (hydroxyl)(phenyl)methylphosphonate；(S)-dibenzyl phenyl(hydroxy)methylphosphonate；dibenzyl hydroxy(phenyl)methane phosphonate；(S)-bis(phenylmethoxy)phosphoryl-phenylmethanol
• 化学式: C₂₁H₂₁O₄P
• 分子量: 368.369
• InChiKey: CXXHOMAIPKBMEZ-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  (+/-)-dibenzyl [hydroxy(phenyl)methyl]phosphonate 在 chiral vanadyl(V) 氧气 作用下， 以 甲苯 为溶剂， 反应 30.0h， 以48%的产率得到(S)-dibenzyl [hydroxy(phenyl)methyl]phosphonate
  参考文献：
  名称：

  带有N-水杨基-α-氨基羧酸盐的手性氧钒(V)甲醇盐催化α-羟基膦酸盐的高对映选择性好氧氧化

  摘要：

  一种前所未有的源自 3,5-二溴-N-水杨酸-1-叔亮氨酸盐的甲醇氧钒络合物 4 能够在环境温度下对 α-羟基膦酸酯进行高度对映选择性有氧氧化，选择性因子范围从 3 到 >99。

  DOI：

  10.1021/ja060639o

文献信息

• Manganese-proline derived new catalyst system for the enantioselective synthesis of α -hydroxyphosphonates and α -aminophosphonates
  作者：Hyun Lim、Vicklyn Datilus、Rania Teriak、Prianka Chohan、Parminder Kaur

  DOI：10.1016/j.tetlet.2017.02.088

  日期：2017.4

  A novel manganese/proline-derived catalyst system is reported for the stereoselective synthesis of α-hydroxyphosphonates and α-aminophosphonates. The reaction proceeded smoothly under mild reaction conditions with efficient reaction times. The resulting products were obtained with high yields and good enantioselectivities (up to 83% ee).

  报道了一种新颖的锰/脯氨酸衍生的催化剂体系，用于α-羟基膦酸酯和α-氨基膦酸酯的立体选择性合成。反应在温和的反应条件下以有效的反应时间顺利进行。得到的产物具有高收率和良好的对映选择性（高达83％ee）。
• Enantioselective C−P Bond Formation through C(<i>sp</i>³)−H Functionalization
  作者：Sandra Ardevines、Devan Horn、Juan V. Alegre‐Requena、Marta González‐Jiménez、M. Concepción Gimeno、Eugenia Marqués‐López、Raquel P. Herrera

  DOI：10.1002/adsc.202300393

  日期：2023.7.4

  An enantioselective C−P bond formation has been developed through a C(sp3)−H activation in an oxidation step followed by an organocatalyzed hydrophosphonylation protocol. The asymmetric organocatalytic Pudovik reaction has been achieved following a one-pot strategy, starting from different benzylic and allylic alcohols and dibenzyl phosphite, using MnO2 as the oxidant and a chiral squaramide as organocatalyst

  通过氧化步骤中的C( sp 3 )−H 活化，然后进行有机催化的氢膦酰化方案，形成了对映选择性 C−P 键。不对称有机催化Pudovik反应是按照一锅法策略实现的，从不同的苄醇和烯丙醇以及亚磷酸二苄酯开始，使用MnO 2作为氧化剂和手性方酰胺作为有机催化剂。该反应范围提供对映体富集的 α-羟基膦酸酯，产率从 40% 到 >95%，对映体选择性从 64% 到 >99%。此外，该方法的使用已被证明可以形成四取代碳立体中心，原位生成苯乙酮衍生物，使用亚磷酸二苯酯。因此，这种方法代表了构建手性 C−P 键的不对称策略，这引起了制药行业的兴趣。
• Highly Enantioselective Hydrophosphonylation of Aldehydes Catalyzed by Tridentate Schiff Base Aluminum(III) Complexes
  作者：Xin Zhou、Xiaohua Liu、Xu Yang、Deju Shang、Junguo Xin、Xiaoming Feng

  DOI：10.1002/anie.200704116

  日期：2008.1
• Kinetic resolution of (±)-diethyl- and dibenzyl hydroxy(phenyl)methanephosphonates and their acyl derivatives with lipases
  作者：Barbara Malinowska、Paulina Majewska、Paweł Szatkowski、Paweł Kafarski、Barbara Lejczak

  DOI：10.3109/10242422.2011.631211

  日期：2011.12

  A wide variety of commercially available lipases and microbial whole cells were tested for biotransformations of (+/-)-diethyl and dibenzyl hydroxyl(phenyl) methanephosphonates. Biocatalytic hydrolysis of acylated hydroxyphosphonates by whole cells of Bacillus subtilis gave optically active compounds with 95% ee (S). Enantioselectivities obtained when using commercially available enzymatic preparations were less satisfactory, leading to both compounds with an enantiomeric excess in the range 15-35%. Screening lipases for their ability to acylate these phosphonates or to hydrolyze their acylated derivatives enabled selection of enzymes and organisms suitable for use in both processes.