Methyl 3-(dimethoxyphosphoryl)but-2-enoate | 232927-72-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl 3-(dimethoxyphosphoryl)but-2-enoate
• 英文别名: (E)-methyl 3-(dimethoxyphosphoryl)but-2-enoate；(E)-methyl 3-methoxyphosphorylbut-2-enoate；methyl (E)-3-dimethoxyphosphorylbut-2-enoate
• CAS: 232927-72-9
• 化学式: C₇H₁₃O₅P
• 分子量: 208.151
• InChiKey: LYSJASBJYRARHO-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  Methyl 3-(dimethoxyphosphoryl)but-2-enoate 在 palladium diacetate 作用下， 以 Petroleum ether 为溶剂， 反应 48.0h， 以78%的产率得到Methyl 3-(dimethoxyphosphoryl)but-3-enoate
  参考文献：
  名称：

  Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

  摘要：

  DOI：

  10.1055/s-1999-3508
• 作为产物：
  描述：

  Methyl 3-hydroxy-3-(dimethoxyphosphoryl)butyrate 在 吡啶 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以34%的产率得到Methyl 3-(dimethoxyphosphoryl)but-2-enoate
  参考文献：
  名称：

  Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

  摘要：

  DOI：

  10.1055/s-1999-3508

文献信息

• Application of the Z-Selective Still–Gennari Olefination Protocol for the Synthesis of Z-α,β-Unsaturated Phosphonates
  作者：Ignacy Janicki、Piotr Kiełbasiński

  DOI：10.1055/s-0037-1609562

  日期：2018.10

  Application of the Z-selective Still–Gennari modification of Horner–Wadsworth–Emmons (HWE) reaction for the olefination of acylphosphonates is presented. A series of new Z-α,β-unsaturated phosphonates containing a carbonyl or ester moiety in the β-position were obtained in up to 94% yield and with up to 96% Z-selectivity. The standard HWE olefination of the acylphosphonates, which was performed for comparison

  摘要 介绍了霍纳-沃兹沃思-埃蒙斯（HWE）反应的Z选择性Still-Gennari修饰在酰基膦酸酯烯化反应中的应用。获得了一系列在β-位含有羰基或酯部分的新型Z -α，β-不饱和膦酸酯，产率高达94％，Z选择性高达96％。进行比较的酰基膦酸酯的标准HWE烯化反应根本不成功，或导致Z选择性差和分离产率较低。 介绍了霍纳-沃兹沃思-埃蒙斯（HWE）反应的Z选择性Still-Gennari修饰在酰基膦酸酯烯化反应中的应用。获得了一系列在β-位含有羰基或酯部分的新型Z -α，β-不饱和膦酸酯，产率高达94％，Z选择性高达96％。进行比较的酰基膦酸酯的标准HWE烯化反应根本不成功，或导致Z选择性差和分离产率较低。
• Asymmetric Bioreduction of β-Activated Vinylphosphonate Derivatives Using Ene-Reductases
  作者：Ignacy Janicki、Piotr Kiełbasiński、Nikolaus G. Turrini、Kurt Faber、Mélanie Hall

  DOI：10.1002/adsc.201700716

  日期：2017.12.11

  thereby providing a stereo‐complementary approach to current asymmetric hydrogenation protocols on similar compounds. Preparative‐scale syntheses performed in aqueous buffer using formate/formate dehydrogenase for recycling of the nicotinamide cofactor granted access to β‐keto‐, cyano‐ and ester phosphonates from the (E)‐isomers of α,β‐unsaturated phosphonates in up to 72% isolated yield and >99% ee.

  通过使用老黄酶家族的几种烯还原酶作为生物催化剂，通过酶促还原相应的β-活化的乙烯基膦酸酯衍生物，获得了一系列功能化的α-手性膦酸酯。单独的膦酸酯基团活化不足，可通过在β位引入吸电子基团来弥补，这导致高水平的转化（高达> 99％）。始终提供所有活性酶（R）配置的产品具有出色的立体选择性，从而为类似化合物的当前不对称氢化方案提供了立体互补方法。使用甲酸/甲酸酯脱氢酶在水性缓冲液中进行制备规模的合成，以回收烟酰胺辅因子，从而可以从多达72种的α，β-不饱和膦酸酯的（E）异构体中获得β-酮，氰基和酯膦酸酯。 ％分离产率和＞ 99％ee。
• Asymmetric Hydrogenation of α,β-Unsaturated Ester- Phosphonates
  作者：Yange Huang、Florian Berthiol、Bart Stegink、Michael M. Pollard、Adriaan J. Minnaard

  DOI：10.1002/adsc.200900051

  日期：2009.6

  Abstractmagnified imageThe rhodium‐catalyzed asymmetric hydrogenation of readily available α,β‐unsaturated ester‐phosphonates affords the corresponding α‐chiral phosphonates in excellent yield and ee. The resulting products are useful multifunctional building blocks applied in the synthesis of physiologically active compounds.
• Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study
  作者：Jens Holz、Renat Kadyrov*、Susanne Borns、Detlef Heller、Armin Börner*

  DOI：10.1016/s0022-328x(00)00071-1

  日期：2000.5

  Studies for controlling rate and enantioselectivity of the asymmetric hydrogenation with Rh-diphosphine catalysts by cooperative attractive interactions within the framework of catalyst-substrate complexes are represented. In strong contrast to a Rh(I)[three-1,4-bis(diphenylphosphino)butane-2,3-diol] catalyst an extremely fast reaction took place applying the complex of the analogue erythro ligand. This is likely due to a strong intramolecular hydrogen bond between the vicinal HO groups impeding the hemilabile coordination of one of the hydroxy groups on the metal center during the hydrogenation. When a substrate with strong hydrogen bond acceptor properties such as (E)-methyl 3-dimethoxyphosphorylbut-2-enoate was hydrogenated even the three catalyst exhibited a fast reaction. The product was obtained in 83% ee. In contrast, when in the ligand both HO groups were replaced by MeO groups only poor conversion and 24% ee were achieved. While with the complex bearing HO groups in methanolic solution the corresponding diastereomeric catalyst substrate complexes were dominant, analogue MeO groups bearing catalyst substrate complexes could not be detected by NMR. For the latter, only the Rh(I)-solvent complex was found revealing the high importance of the additional functional groups on this equilibrium. (C) 2000 Elsevier Science S.A. All rights reserved.