1-isobutyl-3-methyl-3-phospholene 1-oxide | 62891-10-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 1-isobutyl-3-methyl-3-phospholene 1-oxide
• 英文别名: 1-i-butyl-3-methyl-3-phospholene 1-oxide；3-Methyl-1-(2-methylpropyl)-2,5-dihydro-1lambda5-phosphole 1-oxide；3-methyl-1-(2-methylpropyl)-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 62891-10-5
• 化学式: C₉H₁₇OP
• 分子量: 172.207
• InChiKey: YEUFVMJHWWVXSQ-UHFFFAOYSA-N

物化性质

• 沸点：
  309.1±22.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-isobutyl-3-methyl-3-phospholene 1-oxide 在 溴 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 3-Methyl-1-(2-methylpropyl)-1lambda5-phosphole 1-oxide
  参考文献：
  名称：

  利用 P-烷基 2,3-氧杂磷杂双环 [2.2.2] 辛烯 3-氧化物前体对亲核试剂进行片段化相关的膦酰化

  摘要：

  新的 P-烷基 2,3-氧杂磷杂双环-[2.2.2] 辛烯 3-氧化物是通过相应的 7-磷酰冰片烯 7-氧化物的 Bayer-Villiger 氧化合成的，并用作反应性烷基偏膦酸酯的前体，可用于醇的膦酰化. 这是第一个通过 O 插入形成的两种区域异构体的反应性不同的情况，并且在微波辅助条件下实现了导致膦酸酯的断裂相关的膦酰化。

  DOI：

  10.1002/hc.21304
• 作为产物：
  描述：

  1-hydroxy-3-methyl-3-phospholene 1-oxide 在 氯化亚砜 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 生成 1-isobutyl-3-methyl-3-phospholene 1-oxide
  参考文献：
  名称：

  Platinum(II) complexes incorporating racemic and optically active 1-alkyl-3-phospholene P-ligands: Synthesis, stereostructure, NMR properties and catalytic activity

  摘要：

  Three 1-alkyl-3-phospholene 1-oxides, such as the P-ethyl, P-isobutyl and P-isopentyl derivative were prepared in racemic and enantiopure forms. After deoxygenation, the cyclic phosphines were converted to the corresponding phosphine-boranes and phosphine-platinum complexes (PtCl2L2, where L 1-alkyl-3-phospholene). The new products were characterized by spectral methods, and the stereostructure of the complexes was also evaluated by high level quantum chemical calculations. The platinum complexes were tested in the hydroformylation of the styrene. The extent of the regioselectivity towards branched aldehyde exceeds that measured with earlier platinum complexes. However, the enantioselectivity remained below 29%. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.03.045

文献信息

• Dynamic kinetic resolution of 1-substituted-3-methyl-3-phospholene oxides via the formation of diastereomeric alkoxyphospholenium salts
  作者：Péter Bagi、Réka Herbay、Péter Ábrányi-Balogh、Béla Mátravölgyi、Elemér Fogassy、György Keglevich

  DOI：10.1016/j.tet.2018.07.058

  日期：2018.10

  then rearranged into the corresponding optically active 3-phospholene oxides upon heating. After a screening of chiral auxiliaries and the optimization of the reaction conditions, several scalemic 1-aryl- or 1-alkyl-3-methyl-3-phospholene oxides were prepared in excellent yields and with ee-s up to 35%. The key steps of this resolution were investigated by quantum chemical calculations to get some insights

  阐述了一种基于形成共价非对映中间体的动态动力学拆分方法，以制备对映体富集的1-取代-3-甲基-3-氧化膦。首先将3-环氧丙烷氧化物转化为相应的氯-3-磷鎓氯化物。氯磷鎓盐的对映异构体之间的动态相互转化已通过实验验证，因为这是动态拆分的关键步骤。使环状氯代磷鎓盐与带有羟基官能团的手性助剂反应，以不等量形成相应的非对映体烷氧基磷鎓盐。然后在加热时将非对映异构物质重新排列成相应的旋光的3-氧化茂氧化物。在筛选了手性助剂并优化了反应条件后，以极高的收率和高达35％的ee制备了几种规模的1-芳基-或1-烷基-3-甲基-3-膦基环氧丙烷。通过量子化学计算研究了该分辨率的关键步骤，以深入了解造成立体选择的因素。
• Isomerization and application of phospholene oxides
  作者：Réka Herbay、Nikolett Péczka、Gábor Györke、Péter Bagi、Elemér Fogassy、György Keglevich

  DOI：10.1080/10426507.2018.1553043

  日期：2019.5.27

  Abstract In this research, an investigation of the isomerization and the applications of 3-phospholene oxides were elaborated. The isomerization of 3-phospholene oxides to 2-phospholene oxides was investigated under thermal condition. The application of bases and acids was also tested in this reaction. Moreover, the isomerization was also elaborated via the formation of halophosphonium salt intermediates

  摘要 本研究对3-磷烯氧化物的异构化及其应用进行了研究。在热条件下研究了 3-磷烯氧化物异构化为 2-磷烯氧化物。在该反应中还测试了碱和酸的应用。此外，异构化也通过形成卤代鏻盐中间体来进行。3-磷烯氧化物被脱氧并转化为相应的钯配合物。图形概要
• A novel preparation of chlorophospholenium chlorides and their application in the synthesis of phospholene boranes
  作者：Réka Herbay、Péter Bagi、Zoltán Mucsi、Béla Mátravölgyi、László Drahos、Elemér Fogassy、György Keglevich

  DOI：10.1016/j.tetlet.2016.12.059

  日期：2017.2

  A novel preparation of 1-chloro-3-methyl-3-phospholenium chlorides was developed by reacting 1-substituted-3-methyl-3-phospholene 1-oxides with oxalyl chloride. The obtained cyclic chlorophosphonium salts were reacted with LiBH4 to afford the corresponding 1-substituted-3-methyl-3-phospholene boranes. The latter protocol involves a silane-free deoxygenation, and borane complex formation. In one instance

  通过使1-取代的-3-甲基-3-膦-1-氧化物与草酰氯反应，开发了一种新型的1-氯-3-甲基-3-磷酰氯的制备方法。使获得的环状氯盐与LiBH 4反应，得到相应的1-取代的-3-甲基-3-膦基硼烷。后一种方案涉及无硅烷的脱氧和硼烷络合物的形成。在一种情况下，通过在环氯phosph盐中双键的重排来合成2-膦硼烷和相应的P-氧化物。通过量子化学计算研究了这种双键迁移。
• Preparation of 2-phospholene oxides by the isomerization of 3-phospholene oxides
  作者：Péter Bagi、Réka Herbay、Nikolett Péczka、Zoltán Mucsi、István Timári、and György Keglevich

  DOI：10.3762/bjoc.16.75

  日期：——

  obtained by heating the 3-phospholene oxides in methanesulfonic acid, or via the formation of cyclic chlorophosphonium salts. Whereas mixtures of the 2- and 3-phospholene oxides formed, when the isomerization of 3-phospholene oxides was attempted under thermal conditions, or in the presence of a base. The mechanisms of the various double bond migration pathways were elucidated by quantum chemical calculations

  通过双键重排，由相应的3-氧化膦制备一系列1-取代的-3-甲基-2-氧化膦。可以通过在甲磺酸中加热3-氧化膦或通过形成环状氯膦盐来获得2-氧化膦。然而，当在热条件下或在碱的存在下尝试3-环氧丙烷的异构化时，形成了2-环氧丙烷和3-环氧丙烷的混合物。量子化学计算阐明了各种双键迁移途径的机理。
• A Case Study on the Resolution of the 1-<i>i</i>-Butyl-3-methyl-3-phospholene 1-Oxide via Diastereomeric Complex Formation Using TADDOL Derivatives and via Diastereomeric Coordination Complexes Formed from the Calcium Salts of<i>O</i>,<i>O</i>′-Diaroyl-(2<i>R</i>,3<i>R</i>)-tartaric Acids
  作者：Péter Bagi、András Fekete、Mihály Kállay、Dóra Hessz、Miklós Kubinyi、Tamás Holczbauer、Mátyás Czugler、Elemér Fogassy、György Keglevich

  DOI：10.1002/hc.21218

  日期：2015.1

  agent. The absolute configuration of the P-asymmetric center was determined by circular dichroism spectroscopy and related quantum chemical calculations. In one instance, the single crystal of the diastereomeric complex incorporating i-butyl-3-phospholene oxide and spiro-TADDOL was subjected to X-ray analysis, which suggested a feasible hypothesis for the efficiency of the resolution process under discussion

  应用 TADDOL [(-)-(4R,5R)-4,5-双(二苯基羟甲基)-2,2-二甲基二氧戊环]，研究了 1-i-丁基-3-甲基-3-磷烯 1-氧化物的拆分，螺-TADDOL [(-)-(2R,3R)-α,α,α',α'-四苯基-1,4-二氧杂螺[4.5]癸烷-2,3-二甲醇]，或酸性和中性Ca2+盐(-)-O,O'-二苯甲酰基-和(-)-O,O'-二-对甲苯甲酰基-(2R,3R)-酒石酸作为拆分剂。P-不对称中心的绝对构型由圆二色光谱和相关的量子化学计算确定。在一个例子中，对结合了异丁基-3-磷烯氧化物和螺环-TADDOL 的非对映体复合物的单晶进行了 X 射线分析，这为正在讨论的拆分过程的效率提出了一个可行的假设，这可能是“溶剂抑制”分辨率的示例。