(+/-)-1-(acetylamino)-1-dimethylphosphonylethane | 162850-80-8

• 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: (+/-)-1-(acetylamino)-1-dimethylphosphonylethane
• 英文别名: 1-(N-acetylamino)ethylphosphonic acid dimethyl ester；Dimethyl (1-acetamidoethyl)phosphonate；N-(1-dimethoxyphosphorylethyl)acetamide
• CAS: 162850-80-8
• 化学式: C₆H₁₄NO₄P
• 分子量: 195.155
• InChiKey: CPOFFVQWMATARL-UHFFFAOYSA-N

物化性质

• 沸点：
  342.0±25.0 °C(Predicted)
• 密度：
  1.142±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-1-(acetylamino)-1-dimethylphosphonylethane 在 盐酸 、 水 作用下， 反应 2.0h， 以97%的产率得到1-乙酰氨基乙基膦酸
  参考文献：
  名称：

  Penicillin G acylase-mediated kinetic resolution of racemic 1-( N -acylamino)alkylphosphonic and 1-( N -acylamino)alkylphosphinic acids and their esters

  摘要：

  Extensive studies on the penicillin G acylase-mediated kinetic resolution of N-acylated 1-aminoalkylphosphonic and 1-aminoalkylphosphinic acids as well as their esters were carried out to recognise the relationships between the substrate structure, reaction conditions, and the enzymatic hydrolytic deacylation efficiency and stereoselectivity. Reactivity of 1-(N-acylamino)alkylphosphonic and 1-(N-acylamino)allcylphosphinic acids and their esters in the penicillin G acylase-mediated hydrolytic deacylation reaction depends strongly on the kind of their N-acyl group, with high preference to the hydrolytic splitting of the N-phenylacetyl moiety. The initial hydrolysis rates of 1-(N-phenylacetylamino)alkylphosphonic acid dimethyl esters 2 are mostly distinctly lower in comparison with the corresponding free acids 3 and rapidly decrease with the increasing steric effect of the substituent at the alpha-position. In contrary to the substituents at the alpha-carbon, bulky substituents at the phosphorus hinder the enzymatic hydrolysis to a much lesser degree. The penicillin G acylase-mediated stereospecific hydrolysis of N-acyl group of both racemic 1-(N-acylamino)alkylphosphonic acids 3 and their dimethyl esters 2 proved to be, in most cases, a highly effective method for the kinetic resolution of these compounds: High enzyme enantioselectivity E-values exceeding 100, or synthetically useful E-values exceeding 20 (in two cases) were obtained for the N-acylated phosphonic acid analogues of alanine, phenylalanine, valine, leucine, and asparagine, as well as for their dimethyl esters, with the exception of the dimethyl ester of phosphonic analogue of valine 2e, that E-value was low (E=1.2). Also for the N-acylated H-phosphinic acid analogues of alanine, as well as phenylphosphinic acid analogue of alanine, high enzyme enantioselectivity values exceeding 100 were obtained. In contrary, E-values for both diastereomers of ethyl ester of phenylphosphinic analogue of alanine 2k were low (E=7 and 13). For the all accomplished assignments penicillin G acylase exhibited stereochemical preference for the (R)-substrate. (C) 2016 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2016.05.011
• 作为产物：
  描述：

  N-(1-dimethoxyphosphorylethenyl)acetamide 在 [(1,1-bis((i-Pr)2-phosphino)ferrocenyl)Rh(COD)]OTf 氢气 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、405.33 kPa 条件下， 生成 (+/-)-1-(acetylamino)-1-dimethylphosphonylethane
  参考文献：
  名称：

  Enantioselective Synthesis of α-Hydroxy and α-Amino Phosphonates via Catalytic Asymmetric Hydrogenation

  摘要：

  [GRAPHICS]Cationic rhodium catalysts of the C-2 symmetric DuPHOS (1) and BPE (2) ligands have demonstrated the ability to asymmetrically hydrogenate a novel series of enol phosphonates (3) in good to excellent enantiomeric excess under mild conditions. Initial studies toward the catalytic asymmetric hydrogenation of enamido phosphonates (6 and 7) using the DuPHOS-Rh+ catalysts are also reported.

  DOI：

  10.1021/ol9906099

文献信息

• Modular Phosphine-Aminophosphine Ligands Based on Chiral 1,2,3,4-Tetrahydro-1-naphthylamine Backbone: A New Class of Practical Ligands for Enantioselective Hydrogenations
  作者：Min Qiu、Xiang-Ping Hu、Jia-Di Huang、Dao-Yong Wang、Jun Deng、Sai-Bo Yu、Zheng-Chao Duan、Zhuo Zheng

  DOI：10.1002/adsc.200800418

  日期：——

  been achieved in the hydrogenation of most substrates tested, demonstrating the high potential of these newly developed phosphine-aminophosphine ligands in asymmetric catalysis. The present research also discloses that these newly developed phosphine-aminophosphine ligands are more efficient than that derived from (S)-1-phenylethylamine, suggesting that the increased rigidity conferred by a cyclohexyl

  （R）-1,2,3,4-四氢-1-萘胺经两步法制备了一系列新的手性膦-氨基膦配体[（R）-HW-Phos] ，并成功应用于铑催化的各种官能化烯烃的不对称加氢反应，例如α-烯醇酯膦酸酯，α-烯酰胺膦酸酯，（Z）-β-（酰氨基）丙烯酸酯等。在大多数受试底物的氢化反应中，均具有出色的对映选择性，这表明这些新开发的膦-氨基膦配体在不对称催化中具有很高的潜力。本研究还公开了这些新开发的膦-氨基膦配体比衍生自（S）-1-苯基乙胺，表明在这些膦-氨基膦配体中由环己基片段赋予的增加的刚性在不对称诱导中具有积极作用。
• A Facile Conversion of Aminoalkanephosphonic Acids Into O,O-Dialkyl N-Acylaminoalkanephosphonate Derivatives
  作者：Zbigniew H. Kudzin、Jerzy Łuczak

  DOI：10.1055/s-1995-3952

  日期：1995.5

  The facile conversion of aminoalkanephosphonic acids to their O,O-dialkyl N-acylaminoalkanephosphonate derivatives is described.

  本文介绍了将氨基烷基膦酸简便地转化为其 O,O-二烷基 N-酰氨基烷基膦酸衍生物的过程。
• PROCESS FOR PRODUCING PHOSPHORUS-CONTAINING DEHYDROAMINO ACID
  申请人：Kurihara Kenichi

  公开号：US20110009662A1

  公开（公告）日：2011-01-13

  A process for efficiently producing through a small number of steps an N-substituted 2-amino-4-(substituted-oxymethylphosphinyl)-2-butenoic ester which is an intermediate for herbicide L-AMPB. The process comprises reacting a compound represented by the following formula (1): (where R 1 represents C 1-4 alkyl group) with a compound represented by the following formula (2): (wherein R 2 , R 2′ , and R 3 each represents C 1-4 alkyl and R 4 represents benzyloxycarbonyl) in the presence of a base.

  一种高效生产除草剂L-AMPB的中间体N-取代2-氨基-4-(取代氧甲基膦基)-2-丁烯酸酯的方法，仅需少量步骤。该方法包括在碱的存在下将以下式子(1)所代表的化合物(其中R1代表C1-4烷基)与以下式子(2)所代表的化合物反应(其中R2、R2'和R3各代表C1-4烷基，R4代表苄氧羰基)。
• Kudzin, Zbigniew H.; Drabowicz, Jozef; Sochacki, Marek, Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 92, # 1-4, p. 77 - 94
  作者：Kudzin, Zbigniew H.、Drabowicz, Jozef、Sochacki, Marek、Wisniewski, Witold

  DOI：——

  日期：——
• Kudzin Zbigniew H., luczak Jerzy, Synthesis, (1995) N 5, S 509-511
  作者：Kudzin Zbigniew H., luczak Jerzy

  DOI：——

  日期：——