dimethyl (1-acetoxy-2E-butenyl) phosphonate | 128389-06-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: dimethyl (1-acetoxy-2E-butenyl) phosphonate
• 英文别名: <(E)-1-acetoxy-2-butenyl>phosphonsaeure-dimethylester；dimethyl <(E)-1-acetyloxy-2-butenyl>phosphonate；Sdxdjigdtaujmg-aatrikpksa-；[(E)-1-dimethoxyphosphorylbut-2-enyl] acetate
• CAS: 128389-06-0
• 化学式: C₈H₁₅O₅P
• 分子量: 222.178
• InChiKey: SDXDJIGDTAUJMG-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl (1-acetoxy-2E-butenyl) phosphonate 在 二(氰基苯)二氯化钯 作用下， 以 甲苯 为溶剂， 生成 <(E)-3-acetoxy-1-butenyl>phosphonsaeure-dimethylester
  参考文献：
  名称：

  烯丙基羟基膦酸酯的立体选择性反应

  摘要：

  钯催化亲核试剂加成到碳酸酯衍生物的立体化学结果，亚胺酸酯和氨基甲酸酯衍生物的 [3,3] 重排，以及羟基烯丙基膦酸酯的环氧化和环丙烷化。

  DOI：

  10.1080/10426509908546212
• 作为产物：
  描述：

  dimethyl (E)-(1-hydroxybut-2-en-1-yl)phosphonate 、 乙酰氯 在 poly(4-vinyl)pyridine 作用下， 以 乙腈 为溶剂， 以96%的产率得到dimethyl (1-acetoxy-2E-butenyl) phosphonate
  参考文献：
  名称：

  The synthesis of 1-hydroxy phosphonates of high enantiomeric excess using sequential asymmetric reactions: titanium alkoxide-catalyzed PC bond formation and kinetic resolution

  摘要：

  Titanium alkoxide-catalyzed asymmetric phosphonylation of aldehydes yields hydroxy phosphonates in moderate to good enantiomeric excess (e.e.s similar to 70%). The hydroxy phosphonates were acetylated and the acetates were subjected to enzyme-catalyzed kinetic resolution. The non-racemic acetates 2 (predominantly (R)-enantiomer) were hydrolyzed with an (R)-enantiomer-selective lipase, resulting predominantly in the hydrolysis of the (R)-isomer (at 85% conversion) to give the alcohols 3 with high e.e. Alternatively, hydrolysis of the minor enantiomeric (S)-acetate to approximately 20% conversion left the enriched (R)-configured acetate with improved e.e. (> 90%). The moderate enantio selectivities obtained in the catalytic P-C bond formation are enhanced during the enzymatic hydrolysis. Furthermore, availability of the non-racemic phosphonates permits the use of less selective enzymes, resulting in higher yields in comparison with the standard resolution of racemic materials. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00303-2

文献信息

• Enzymes in organic chemistry, part 1: Enantioselective hydrolysis of α-(acyloxy)phosphonates by esterolytic enzymes
  作者：Yong-Fu Li、Friedrich Hammerschmidt

  DOI：10.1016/s0957-4166(00)86021-8

  日期：1993.1

  exclusively hydrolyzed to give optically pure alcohols (S)-(−)-3a and (S)-(−)-3b. Lipases AP 6 and F-AP 15 were used to prepare phosphonates (S)-(−)-3b, (S)-(+)-3d and (S)-(−)-3e on a preparative scale with an enantiomeric excess of 81%, 87%, and 89%, respectively. The absolute configurations ofthe α-hydroxyphosphonates were assigned by Horeau's method and 1H-NMR spectroscopy of Mosher's derivatives

  制备α-羟基膦酸酯（±）-3并转化为酯（±）-5。测试了八种脂肪酶以及猪肝酯酶，作为双相系统中α-（酰氧基）膦酸酯的对映选择性水解的催化剂。他们中的两个被证明是有用的。以脂肪酶F-AP 15和α-（乙酰氧基）苯基甲基膦酸酯（±）-5a和（±）-5b为底物可获得最高的对映选择性。（S）-对映异构体专门水解，得到光学纯的醇（S）-（-）- 3a和（S）-（-）- 3b。脂肪酶AP 6和F-AP 15用于制备膦酸酯（S）-（-）- 3b，（S）-（+）- 3d和（S）-（-）- 3e在制备规模上，对映体过量分别为81％，87％和89％。α-羟基膦酸酯的绝对构型通过Horeau法和Mosher衍生物的1 H-NMR光谱确定。
• Oehler, Elisabeth; Zbiral, Erich, Chemische Berichte, 1991, vol. 124, # 1, p. 175 - 184
  作者：Oehler, Elisabeth、Zbiral, Erich

  DOI：——

  日期：——
• OHLER, ELISABETH;ZBIRAL, ERICH, CHEM. BER., 124,(1991) N, C. 175-184
  作者：OHLER, ELISABETH、ZBIRAL, ERICH

  DOI：——

  日期：——

表征谱图