dimethyl (E)-(1-hydroxybut-2-en-1-yl)phosphonate | 128412-18-0

• 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 (E)-(1-hydroxybut-2-en-1-yl)phosphonate
• 英文别名: (+/-)-dimethyl (1-hydroxy-2E-butenyl) phosphonate；dimethyl (1-hydroxy-2-butenyl)phosphonate；(E)-1-dimethoxyphosphorylbut-2-en-1-ol
• CAS: 128412-18-0
• 化学式: C₆H₁₃O₄P
• 分子量: 180.141
• InChiKey: ZTFCKDGCKRVFED-SNAWJCMRSA-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：

  dimethyl (E)-(1-hydroxybut-2-en-1-yl)phosphonate 在 三氧化硫吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 1.0h， 以372 mg的产率得到dimethyl (E)-but-2-enoylphosphonate
  参考文献：
  名称：

  烷基芳基烯酮与 β,γ-不饱和 α-酮膦酸酯的对映选择性 NHC 催化的 [4+2] 环加成反应

  摘要：

  描述了 NHC 介导的对映选择性形式 [4+2] 烷芳基烯酮与 γ-取代-β,γ-不饱和 α-酮膦酸酯的环加成反应。观察到非对映选择性的底物依赖性转换，γ-芳基α-酮膦酸酯优先提供顺式二氢吡喃酮膦酸酯和γ-甲基α-酮膦酸酯，有利于抗二氢吡喃酮膦酸酯。此外，与相应的两步法相比，原位生成乙烯酮保留了高水平的立体选择性并提高了产品收率。

  DOI：

  10.1055/s-0033-1338851
• 作为产物：
  描述：

  亚磷酸氢二甲酯 、 丁烯-2-醛 在 titanium(IV) isopropylate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以89%的产率得到dimethyl (E)-(1-hydroxybut-2-en-1-yl)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

• Stereospecific Pd(O)-Catalyzed Malonate Additions to Allylic Hydroxy Phosphonate Derivatives:  A Formal Synthesis of (−)-Enterolactone
  作者：Bingli Yan、Christopher D. Spilling

  DOI：10.1021/jo035795h

  日期：2004.4.1

  A combination of cross-metathesis and malonate addition was applied to a formal synthesis of the mammalian lignan enterolactone 5. The cross-metathesis of alkene 6 and phosphonate 3a gave the substituted allylic phosphonate 3d. The palladium-catalyzed addition of malonate 10d to the allylic phosphonate 3d was stereospecific and highly regioselective and yielded the vinyl phosphonate 11d. The vinyl

  交叉复分解和丙二酸酯添加的组合应用于哺乳动物木脂体肠内酯5的正式合成。烯烃6和膦酸酯3a的交叉复分解得到取代的烯丙基膦酸酯3d。钯催化的丙二酸酯10d向烯丙基膦酸酯3d的加成是立体特异性的，且具有高度区域选择性，并生成乙烯基膦酸酯11d。膦酸乙烯基酯11d分两步转化为内酯14，内酯14是肠内酯5合成中已知的中间体。
• 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）。
• Synthesis of Nonracemic Allylic Hydroxy Phosphonates via Alkene Cross Metathesis
  作者：Anyu He、Bingli Yan、Anchalee Thanavaro、Christopher D. Spilling、Nigam P. Rath

  DOI：10.1021/jo0490090

  日期：2004.12.1

  their derivatives can be interconverted by using cross metathesis with second generation Grubbs catalyst. The absolute stereochemistry of the starting phosphonate is conserved in the product. Cross metathesis reaction of the acrolein-derived phosphonate 2a yields a series of functionalized allylic hydroxy phosphonates. However, the cross metathesis reaction is often accompanied by competing dimerization

  烯丙基羟基膦酸酯及其衍生物可通过与第二代Grubbs催化剂进行交叉复分解而相互转化。起始膦酸酯的绝对立体化学在产物中是保守的。丙烯醛衍生的膦酸酯2a的交叉复分解反应产生一系列官能化的烯丙基羟基膦酸酯。然而，交叉复分解反应通常伴随竞争性二聚化和烯烃迁移反应，从而导致产率降低。还检查了肉桂醛和巴豆醛衍生的膦酸酯2b和2c。通常，膦酸酯2b和2c的复分解反应比膦酸酯的复分解反应要慢得多。2a导致混合。膦酸酯2a的几种羟基保护衍生物（碳酸甲酯3a，乙酸酯4a，氨基甲酸N-甲苯磺酯5a，TBDMS 6a和乙酰乙酸酯7a）进行复分解而不会发生竞争性副反应，从而以高至优异的收率得到取代的烯丙基膦酸酯。
• SYNTHESIS OF PHOSPHONIC ACIDS RELATED TO THE ANTIBIOTIC FOSMIDOMYCIN FROM ALLYLIC α- AND γ-HYDROXYPHOSPHONATES
  作者：Elisabeth Öhler、Silvia Kanzler

  DOI：10.1080/10426509608046350

  日期：1996.5.1

  high (E)-stereoselectivity to give the protected (3-N-hydroxyamino-1-alkenyl)-phosphonates 5 and 6, respectively, with very good yields. Alternatively compounds 5 and 6 are obtained in excellent yields from the (3-hydroxy-l-alkenyl)phosphonates 2 under Mitsunobu conditions using 3a and 3b, respectively, as nucleophiles. Much less satisfactory yields of compounds 7 and 8 have been obtained in both pathways

  摘要 Pd(O) 催化二烷基 (1-甲氧基羰基氧基-2-烯基) 膦酸酯 4 (R3 = H) 与 N,O-烷氧基羰基保护的羟胺 BocNHOBoc (3a) 和 MocNHOMoc (3b) 进行区域特异性和高 (E )-立体选择性，分别得到受保护的 (3-N-羟基氨基-1-烯基)-膦酸酯 5 和 6，产率非常好。或者，在Mitsunobu条件下，分别使用3a和3b作为亲核试剂，由(3-羟基-1-烯基)膦酸酯2以优异的产率获得化合物5和6。在分别使用羟胺衍生物 BocNHOBn (3c) 和 AcNHOAc (3d) 作为亲核试剂的两种途径中，化合物 7 和 8 的产率都不太令人满意。
• 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。