diethyl 2-oxo-hept-6-enephosphonate | 123444-56-4

• 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: diethyl 2-oxo-hept-6-enephosphonate
• 英文别名: Diethyl (2-oxohept-6-en-1-yl)phosphonate；1-diethoxyphosphorylhept-6-en-2-one
• CAS: 123444-56-4
• 化学式: C₁₁H₂₁O₄P
• 分子量: 248.259
• InChiKey: ZMPBHMRPTVAUHT-UHFFFAOYSA-N

物化性质

• 沸点：
  334.0±35.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-oxo-hept-6-enephosphonate 生成 2-Diethoxyphosphoryl-3-carboxy-cyclopentanone
  参考文献：
  名称：

  Mikolajczyk, Marian; Kielbasinski, Piotr; Zurawinski, Remigtusz, Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 97 - 100

  摘要：

  DOI：
• 作为产物：
  描述：

  甲基膦酸二乙酯 在 copper(l) iodide 、 正丁基锂 、 sodium hydride 作用下， 生成 diethyl 2-oxo-hept-6-enephosphonate
  参考文献：
  名称：

  One pot synthesis of mono- and spirocyclic α-phosphonato-α,β-unsaturated cycloenones

  摘要：

  A one pot ozonolysis/intramolecular aldol condensation (with the aid of TsOH and Et3N as catalysts) of beta-keto-omega-alkenylphosphonates provided the alpha-phosphonato-alpha,beta-unsaturated cycloenone with good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00460-2

文献信息

• Total Synthesis of Racemic and Optically Active Sarkomycin
  作者：Marian Mikołajczyk、Remigiusz Żurawiński、Piotr Kiełbasiński、Michał W. Wieczorek、Jarosław Błaszczyk、Wiesław R. Majzner

  DOI：10.1055/s-1997-1193

  日期：1997.3

  trans-3-Carboxy-2-diethoxyphosphorylcyclopentanone (11), a key precursor of sarkomycin 1, has been synthesized in the rhodium(II) acetate promoted cyclization of diethyl 1-diazo-2-oxohept-6-enephosphonate (9), followed by transformation of the 3-vinyl moiety into the 3-carboxylic group. Racemic 11 has been resolved into enantiomers via diastereoisomeric enamine-type derivatives 13 resulting from its reaction with (-)-(S)-1-(1-naphthyl)ethylamine. The structure and absolute configuration of 13 have been determined by X-ray crystal structure analysis. The enantiomerically enriched (up to 77.6% ee) acid 11 has also been obtained in the enzyme-promoted hydrolysis of racemic 2-diethyoxyphosphoryl-3-methoxycarbonylcyclopentanone (12). The Horner-Wittig reaction of 11 with gaseous formaldehyde has been applied to introduce the exocyclic α-methylene moiety into the cyclopentanone system and thus to complete the synthesis of the racemate and, for the first time, each enantiomer of sarkomycin 1. A phenomenon of enantiomer self-discrimination has been observed in 31PNMR spectra of the nonracemic acid 11 and explained in terms of the formation of the hydrogen bonded homo- and hetero-dimers. The existence of dimeric structures has been confirmed by X-ray analysis of the structurally closely related trans-3-carboxy-2-diphenylphosphinoyl-cyclopentanone (16).

  反式-3-羧基-2-二乙氧基磷酰环戊酮（11）是沙考霉素 1 的关键前体，它是在 1-重氮-2-氧代庚基-6-烯基膦酸二乙酯（9）的乙酸铑（II）促进环化反应中合成的，随后 3-乙烯基转变为 3-羧基。外消旋 11 与(-)-(S)-1-(1-萘基)乙胺反应生成的非对映异构体烯胺类衍生物 13 将外消旋 11 分解成对映体。通过 X 射线晶体结构分析确定了 13 的结构和绝对构型。外消旋 2-二乙氧基磷酰-3-甲氧羰基环戊酮（12）在酶促水解过程中也得到了对映体富集（ee高达 77.6%）的酸 11。11 与气态甲醛的霍纳-维蒂希反应被用于将外环δ-亚甲基引入环戊酮体系，从而完成了外消旋体的合成，并首次合成了沙可霉素 1 的各对映体。通过对结构上密切相关的反式-3-羧基-2-二苯基膦酰基环戊酮（16）进行 X 射线分析，证实了二聚体结构的存在。
• A new synthesis of (±)-sarkomycin from a β-ketophosphonate
  作者：Marian Mikołajczyk、Remigiusz Zurawiński、Piotr Kiełbasiński

  DOI：10.1016/s0040-4039(01)80382-8

  日期：1989.1

  The total synthesis of (±)-sarkomycin starting from diethyl 2-oxopropanephosphonate is reported. The key step in this synthesis includes the Horner-Wittig reaction of 2-diethoxy-phosphoryl-3-carboxy-cyclopentanone with formaldehyde

  报道了从2-氧代丙烷膦酸二乙酯开始的（±）-沙克霉素的全合成。合成的关键步骤包括2-二乙氧基-磷酰基-3-羧基-环戊酮与甲醛的霍纳-维蒂希反应
• MIKOLAJCZYK, MARIAN;ZURAWINSKI, REMIGIUSZ;KIELBASINSKI, PIOTR, TETRAHEDRON LETT., 30,(1989) N, C. 1143-1146
  作者：MIKOLAJCZYK, MARIAN、ZURAWINSKI, REMIGIUSZ、KIELBASINSKI, PIOTR

  DOI：——

  日期：——
• One pot synthesis of mono- and spirocyclic α-phosphonato-α,β-unsaturated cycloenones
  作者：Jun Mo Gil、Jung Hwan Hah、Kwang Young Park、Dong Young Oh

  DOI：10.1016/s0040-4039(98)00460-2

  日期：1998.5

  A one pot ozonolysis/intramolecular aldol condensation (with the aid of TsOH and Et3N as catalysts) of beta-keto-omega-alkenylphosphonates provided the alpha-phosphonato-alpha,beta-unsaturated cycloenone with good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Mikolajczyk, Marian; Kielbasinski, Piotr; Zurawinski, Remigtusz, Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 97 - 100
  作者：Mikolajczyk, Marian、Kielbasinski, Piotr、Zurawinski, Remigtusz、Wieczorek, Michal W.

  DOI：——

  日期：——