(1S,2E)-dimethyl(1-hydroxy-2-butenyl)phosphonate | 147731-07-5

• 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: (1S,2E)-dimethyl(1-hydroxy-2-butenyl)phosphonate
• 英文别名: (E,1S)-1-dimethoxyphosphorylbut-2-en-1-ol
• CAS: 147731-07-5
• 化学式: C₆H₁₃O₄P
• 分子量: 180.141
• InChiKey: ZTFCKDGCKRVFED-OVCGOVNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2E)-dimethyl(1-hydroxy-2-butenyl)phosphonate 在 吡啶 、 N-甲基吡咯烷酮 、 4-二甲氨基吡啶 、 硼烷四氢呋喃络合物 、 tris(dibenzylideneacetone)dipalladium (0) 、 三(2-呋喃基)膦 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 6.0h， 生成 (3R)-dimethyl[1-hydroxy-3-(p-tolyl)butyl]phosphonate
  参考文献：
  名称：

  Stereospecific Pd(0)-Catalyzed Arylation of an Allylic Hydroxy Phosphonate Derivative:  Formal Synthesis of (S)-(+)-ar-Turmerone

  摘要：

  Reaction of the (1S)-allylic hydroxy phosphonate 1(S) with methyl chloroformate in pyridine yields the corresponding carbonate 3(S). The carbonate 3(S) undergoes a palladium-catalyzed arylation with p-tolyl tributylstannane to give both the 1E and 1Z vinyl phosphonates 6 (85:15). The E and Z vinyl phosphonates 6 were shown to have the opposite configuration at C-3. The major vinyl phosphonate isomer (3S,1E), was converted to (3S)-3-(p-tolyl)-butanal 8(S), completing a formal total synthesis of (S)-ar-turmerone 5a.

  DOI：

  10.1021/jo0351318
• 作为产物：
  描述：

  dimethyl (E)-(1-hydroxybut-2-en-1-yl)phosphonate 生成 (1S,2E)-dimethyl(1-hydroxy-2-butenyl)phosphonate
  参考文献：
  名称：

  有机化学中的酶，第1部分：酯水解酶对α-（酰氧基）膦酸酯的对映选择性水解

  摘要：

  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。

  DOI：

  10.1016/s0957-4166(00)86021-8

文献信息

• Allylic hydroxy phosphonates: versatile chiral building blocks
  作者：Antonette De la Cruz、Anyu He、Anchalee Thanavaro、Bingli Yan、Christopher D. Spilling、Nigam P. Rath

  DOI：10.1016/j.jorganchem.2004.11.019

  日期：2005.5

  substituted amino phosphonates using a series of palladium-catalyzed reactions. The judicious selection of nitrogen nucleophile and palladium catalyst allow for excellent regio- and stereochemical control. Palladium(0)-catalyzed amine addition or tosyl carbamate rearrangement gives rise to the γ-substituted phosphonates, whereas, reaction of tosyl carbamates with palladium (II) and base gives oxazolidinones

  使用一系列钯催化的反应，将烯丙基羟基膦酸酯转化为β和γ取代的氨基膦酸酯。氮亲核试剂和钯催化剂的明智选择可以实现出色的区域和立体化学控制。钯（0）催化的胺加成或甲苯磺酸氨基甲酸酯重排产生γ-取代的膦酸酯，而甲苯磺酸氨基甲酸酯与钯（II）和碱的反应产生恶唑烷酮（β-取代）。
• Formation of Cyclic Acetals from Allylic Hydroxy Phosphonates via Intramolecular Oxymercuration
  作者：Anchalee Thanavaro、Christopher D. Spilling

  DOI：10.1080/10426500212221

  日期：2002.6.1

  diastereo- and regio-selectivity. 31 P NMR studies showed the formation of an intermediate hemiacetal and rapid formation of the organomercurial upon addition of mercuric trifluoroacetate. However, the oxymercuration was reversible, and attempts to remove the excess aldehyde often led to recovery of the starting material. Fortunately, reduction of the organomercurial intermediate with sodium cyanoborohydride

  用三氟乙酸汞在醛溶液中处理烯丙基羟基膦酸酯，然后还原有机汞中间体，得到环状缩醛衍生物。该反应显示出高的非对映选择性和区域选择性。31 P NMR 研究表明，加入三氟乙酸汞后，中间体半缩醛的形成和有机汞醛的快速形成。然而，氧汞化是可逆的，并且试图去除过量的醛通常会导致原材料的回收。幸运的是，在醛的存在下用氰基硼氢化钠还原有机汞中间体导致了更高的重现性产率。
• New homochiral cyclic diol ligands for titanium alkoxide catalyzed phosphonylation of aldehydes
  作者：Michael D. Groaning、Bradley J. Rowe、Christopher D. Spilling

  DOI：10.1016/s0040-4039(98)01139-3

  日期：1998.7

  An investigation of the structural effects of chiral diol ligands on the enantioselectivity of phosphorylation was performed. Cyclic diols, and cyclohexanediol in particular, were identified as effective ligands for titanium alkoxide catalyzed asymmetric phosphorylation. (C) 1998 Elsevier Science Ltd. All rights reserved.
• 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。
• Stereospecific Pd(0)-Catalyzed Arylation of an Allylic Hydroxy Phosphonate Derivative:  Formal Synthesis of (<i>S</i>)-(+)-ar-Turmerone
  作者：Bradley J. Rowe、Christopher D. Spilling

  DOI：10.1021/jo0351318

  日期：2003.11.1

  Reaction of the (1S)-allylic hydroxy phosphonate 1(S) with methyl chloroformate in pyridine yields the corresponding carbonate 3(S). The carbonate 3(S) undergoes a palladium-catalyzed arylation with p-tolyl tributylstannane to give both the 1E and 1Z vinyl phosphonates 6 (85:15). The E and Z vinyl phosphonates 6 were shown to have the opposite configuration at C-3. The major vinyl phosphonate isomer (3S,1E), was converted to (3S)-3-(p-tolyl)-butanal 8(S), completing a formal total synthesis of (S)-ar-turmerone 5a.