dimethyl (1S,2S)-2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonate | 294842-98-1

• 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: dimethyl (1S,2S)-2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonate
• 英文别名: dimethyl (1S,2S)-[2-(N-Boc-amino)-1-hydroxy-2-phenylethyl]phosphonate；tert-butyl N-[(1S,2S)-2-dimethoxyphosphoryl-2-hydroxy-1-phenylethyl]carbamate
• CAS: 294842-98-1
• 化学式: C₁₅H₂₄NO₆P
• 分子量: 345.332
• InChiKey: JNMZLHDWURHJRN-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  94.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl (1S,2S)-2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonate 在 盐酸 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 3.0h， 生成 dimethyl (1S,2S)-2-(benzoylamino)-1-hydroxy-2-phenylethylphosphonate
  参考文献：
  名称：

  Enantiomeric phosphonate analogs of the docetaxel C-13 side chain

  摘要：

  Addition of dimethyl phosphite to racemic N-Boc-phenylglycinal led to a 75:25 mixture of syn and anti dimethyl 2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonates. The syn-diastereoisomer was obtained in 50% yield after a single crystallization. Resolution of the syn-isomer was achieved via the (S)-O-methylmandelate esters. Racemization-free ammonolysis gave both enantiomers in high enantiomeric excess. Benzoates of both N-Boc syn-enantiomers were transformed into dimethyl (IR,2R)- and (1S,2S)-2-(benzoylamino)-1-hydroxy-2-phenylethylphosphonates in good yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00203-2
• 作为产物：
  描述：

  膦酸,(2-羰基-2-苯基乙基)-,二甲基酯 在 4-二甲氨基吡啶 、 potassium cyanide 、 甲酸 、 (1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[(S,S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine] 、 水 、 对甲苯磺酸 、 三乙胺 、 cesium fluoride 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 12.5h， 生成 dimethyl (1S,2S)-2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonate
  参考文献：
  名称：

  Rh伴随动态动力学拆分的Rh催化不对称转移加氢立体选择性合成4-取代的5-磺酸氨基磺酸环酯。

  摘要：

  由动态动力学拆分驱动的4-取代的环状氨基磺酸亚胺-5-膦酸酯的不对称转移氢化反应生成了相应的环状氨基磺酸5-膦酸酯。该方法使用HCO 2 H / Et 3 N混合物作为氢源和手性Rh催化剂（（R，R）-或（S，S）-Cp * RhCl（TsDPEN） 1 h具有高收率和高水平的立体选择性。

  DOI：

  10.1021/acs.joc.5b01434

文献信息

• Enantiomerically pure N-Boc- and N-benzoyl-(S)-phenylglycinals
  作者：Andrzej E. Wróblewski、Dorota G. Piotrowska

  DOI：10.1016/s0957-4166(02)00656-0

  日期：2002.11

  Enantionterically pure N-Boc- and N-benzoyl-(S)-phenylglycinals were prepared by oxidation of the respective alcohols with Dess-Martin periodinane. The glycinals were phosphonylated with lithium O,O-dimethyl phosphonate at -70degreesC or (MeO)(2)POTMS at -20degreesC without racemisation. In the presence of 10 mol% of NEt3 at 20degreesC the aldehydes racemised instantaneously, while it, took a few hours for the reacemisation processes to reach completion after addition of 1 mol% of NEt3. (C) 2002 Published by Elsevier Science Ltd.
• Stereochemistry of the addition of dialkyl phosphites to (S)-N,N-dibenzylphenylglycinal
  作者：Andrzej E. Wróblewski、Dorota G. Piotrowska

  DOI：10.1016/s0957-4166(01)00526-2

  日期：2001.11

  The addition of various dialkyl phosphite derivatives to (S)-N,N-dibenzylphenylglycinal 6 led to the preponderance of anti over syn diastereoisomers: from 75:25 when NEt3 or Ti(OiPr)(4) were used to 51:49 for Li or Mg salts. In the NEt3-catalysed reaction, partially racemised phosphonates were formed, while enantiomeric products were obtained after addition of lithium O,O-dimethylphosphonate to (S)-6 at -70degreesC. Because the syn-isomers were found to be resistant to O-benzoylation, Mixtures of diastereoisomers were easily separated after esterification of the anti products. Hydrogenation of the syn-phosphonates in the presence of Boc(2)O gave enantiomeric dialkyl N-Boc-2-amino-1-hydroxy-2-phenylethylphosphonates-phosphonate analogues of the docetaxel C-13 side chain. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Stereoselective Synthesis of 4-Substituted Cyclic Sulfamidate-5-Phosphonates by Using Rh-Catalyzed, Asymmetric Transfer Hydrogenation with Accompanying Dynamic Kinetic Resolution
  作者：Yeon Ji Seo、Jin-ah Kim、Hyeon-Kyu Lee

  DOI：10.1021/acs.joc.5b01434

  日期：2015.9.4

  asymmetric transfer hydrogenation of 4-substituted cyclic sulfamidate imine-5-phosphonates produces the corresponding cyclic sulfamidate-5-phosphonates. The process employs a HCO2H/Et3N mixture as the hydrogen source and the chiral Rh catalysts, (R,R)- or (S,S)-Cp*RhCl(TsDPEN), and it takes place at room temperature within 1 h with high yields and high levels of stereoselectivity.

  由动态动力学拆分驱动的4-取代的环状氨基磺酸亚胺-5-膦酸酯的不对称转移氢化反应生成了相应的环状氨基磺酸5-膦酸酯。该方法使用HCO 2 H / Et 3 N混合物作为氢源和手性Rh催化剂（（R，R）-或（S，S）-Cp * RhCl（TsDPEN） 1 h具有高收率和高水平的立体选择性。
• Enantiomeric phosphonate analogs of the docetaxel C-13 side chain
  作者：Andrzej E Wróblewski、Dorota G Piotrowska

  DOI：10.1016/s0957-4166(00)00203-2

  日期：2000.6

  Addition of dimethyl phosphite to racemic N-Boc-phenylglycinal led to a 75:25 mixture of syn and anti dimethyl 2-[(tert-butoxycarbonyl)amino]-1-hydroxy-2-phenylethylphosphonates. The syn-diastereoisomer was obtained in 50% yield after a single crystallization. Resolution of the syn-isomer was achieved via the (S)-O-methylmandelate esters. Racemization-free ammonolysis gave both enantiomers in high enantiomeric excess. Benzoates of both N-Boc syn-enantiomers were transformed into dimethyl (IR,2R)- and (1S,2S)-2-(benzoylamino)-1-hydroxy-2-phenylethylphosphonates in good yields. (C) 2000 Elsevier Science Ltd. All rights reserved.