(+)-(R)-1-isobutyl-3-methyl-3-phospholene 1-oxide | 1548599-09-2

• 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: (+)-(R)-1-isobutyl-3-methyl-3-phospholene 1-oxide
• 英文别名: (R)-1-i-butyl-3-methyl-3-phospholene 1-oxide；(1R)-3-methyl-1-(2-methylpropyl)-2,5-dihydro-1lambda5-phosphole 1-oxide；(1R)-3-methyl-1-(2-methylpropyl)-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 1548599-09-2
• 化学式: C₉H₁₇OP
• 分子量: 172.207
• InChiKey: YEUFVMJHWWVXSQ-NSHDSACASA-N

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：

  (+)-(R)-1-isobutyl-3-methyl-3-phospholene 1-oxide 在 三氯硅烷 作用下， 以 甲苯 为溶剂， 反应 6.0h， 生成
  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
• 作为产物：
  描述：

  1-hydroxy-3-methyl-3-phospholene 1-oxide 在 氯化亚砜 、 (-)-(2R,3R)-trans-2,3-bis(hydroxydiphenylmethyl)-1,4-dioxaspiro[4.5]decane 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 为溶剂， 反应 24.0h， 生成 (+)-(R)-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。
• 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。