5-(Diethoxyphosphinyl)-3-methylcyclopent-2-en-1-one | 136213-63-3

• 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: 5-(Diethoxyphosphinyl)-3-methylcyclopent-2-en-1-one
• 英文别名: 5-Diethoxyphosphoryl-3-methylcyclopent-2-en-1-one
• CAS: 136213-63-3
• 化学式: C₁₀H₁₇O₄P
• 分子量: 232.216
• InChiKey: ZHEVAXRQOOCOFD-UHFFFAOYSA-N

物化性质

• 沸点：
  344.1±42.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  N-羟基氨基甲酸叔丁酯 、 5-(Diethoxyphosphinyl)-3-methylcyclopent-2-en-1-one 在 manganese(IV) oxide 、 copper(II) bis(trifluoromethanesulfonate) 、 (R,R)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 16.0h， 以80%的产率得到tert-butyl N-[(1R)-1-diethoxyphosphoryl-4-methyl-2-oxocyclopent-3-en-1-yl]oxycarbamate
  参考文献：
  名称：

  以原位生成的亚硝基羰基化合物为氧源的铜催化不对称合成叔α-羟基膦酸衍生物

  摘要：

  α-羟基膦酸及其衍生物是具有高生物活性的结构基序。据报道，这些化合物可通过原位生成的亚硝基羰基化合物作为亲电子氧源，通过铜催化的β-酮膦酸酯的直接α-氧化而获得。对于环状和非环状底物，这些反应均以高产率（最高95％）和对映选择性（最高> 99％ee）进行。该方法还用于合成α，β-二羟基膦酸酯和β-氨基-α-羟基膦酸酯。

  DOI：

  10.1002/anie.201408893
• 作为产物：
  描述：

  二乙基亚磷酰氯 、 3-甲基-2-环戊烯-1-酮 生成 5-(Diethoxyphosphinyl)-3-methylcyclopent-2-en-1-one
  参考文献：
  名称：

  Reaction of diethyl phosphorochloridite with enolates: a general method for synthesis of .beta.-keto phosphonates and .alpha.-phosphono esters through carbon-phosphorus bond formation

  摘要：

  The reaction of ketone enolates with diethyl phosphorochloridite, followed by air oxidation of the immediate reaction products, has proven to be a general and convenient method for preparation of beta-keto phosphonates. Fourteen beta-keto phosphonates have been prepared by this method, in an average yield greater than 60%. This procedure also appears to be applicable to preparation of both alpha-phosphono aldehydes and alpha-phosphono esters. Although special precautions may be necessary to avoid aldol condensation during formation of aldehyde enolates, in two cases it was shown that the resulting enolates react readily with diethyl chlorophosphite. Finally, a set of five ethyl esters was converted to alpha-phosphono esters by this method. Yields of the alpha-phosphono esters are influenced by steric hindrance at the enolate carbon, but the average yield for this series was ca. 70%. Because this synthetic method relies upon an electrophilic phosphorus reagent for formation of the C-P bond, it is complementary to the traditional Arbuzov synthesis. On the basis of the 21 examples presented here, it appears to be more widely applicable.

  DOI：

  10.1021/jo00019a016

文献信息

• Copper-Catalyzed Asymmetric Synthesis of Tertiary α-Hydroxy Phosphonic Acid Derivatives with In Situ Generated Nitrosocarbonyl Compounds as the Oxygen Source
  作者：Biplab Maji、Hisashi Yamamoto

  DOI：10.1002/anie.201408893

  日期：2014.12.22

  α‐Hydroxy phosphonic acids and their derivatives are highly bioactive structural motifs. It is now reported that these compounds can be accessed through the copper‐catalyzed direct α‐oxidation of β‐ketophosphonates using in situ generated nitrosocarbonyl compounds as an electrophilic oxygen source. These reactions proceeded in high yields (up to 95 %) and enantioselectivities (up to >99 % ee) for both

  α-羟基膦酸及其衍生物是具有高生物活性的结构基序。据报道，这些化合物可通过原位生成的亚硝基羰基化合物作为亲电子氧源，通过铜催化的β-酮膦酸酯的直接α-氧化而获得。对于环状和非环状底物，这些反应均以高产率（最高95％）和对映选择性（最高> 99％ee）进行。该方法还用于合成α，β-二羟基膦酸酯和β-氨基-α-羟基膦酸酯。
• Reaction of diethyl phosphorochloridite with enolates: a general method for synthesis of .beta.-keto phosphonates and .alpha.-phosphono esters through carbon-phosphorus bond formation
  作者：Koo Lee、David F. Wiemer

  DOI：10.1021/jo00019a016

  日期：1991.9

  The reaction of ketone enolates with diethyl phosphorochloridite, followed by air oxidation of the immediate reaction products, has proven to be a general and convenient method for preparation of beta-keto phosphonates. Fourteen beta-keto phosphonates have been prepared by this method, in an average yield greater than 60%. This procedure also appears to be applicable to preparation of both alpha-phosphono aldehydes and alpha-phosphono esters. Although special precautions may be necessary to avoid aldol condensation during formation of aldehyde enolates, in two cases it was shown that the resulting enolates react readily with diethyl chlorophosphite. Finally, a set of five ethyl esters was converted to alpha-phosphono esters by this method. Yields of the alpha-phosphono esters are influenced by steric hindrance at the enolate carbon, but the average yield for this series was ca. 70%. Because this synthetic method relies upon an electrophilic phosphorus reagent for formation of the C-P bond, it is complementary to the traditional Arbuzov synthesis. On the basis of the 21 examples presented here, it appears to be more widely applicable.
• Asymmetric Synthesis of Tertiary α-Hydroxy Phosphonic Acid Derivatives under Aerobic Oxidation Conditions
  作者：Biplab Maji、Hisashi Yamamoto

  DOI：10.1055/s-0034-1380290

  日期：——

  The copper-catalyzed asymmetric α-hydroxylation of β-ketophosphonates, using in situ generated nitrosocarbonyl compounds as electrophilic source of oxygen, is reported. The reaction merges aerobic oxidation and Lewis acid catalysis. α-Aminoxy-β-ketophosphonates were synthesized in high yields (up to 97% yield) and high enantioselectivities (up to >99% ee).

  报道了铜催化的 β-酮膦酸酯的不对称 α-羟基化，使用原位生成的亚硝基羰基化合物作为氧的亲电源。该反应结合了好氧氧化和路易斯酸催化。以高产率（高达 97% 的产率）和高对映选择性（高达 >99% ee）合成了 α-氨基氧基-β-酮膦酸酯。