(+/-)-1-r-oxo-1,2-c,5-t-triphenylphospholane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+/-)-1-r-oxo-1,2-c,5-t-triphenylphospholane
• 英文别名: (2R,5R)-1,2,5-triphenyl-1λ5-phospholane 1-oxide
• 化学式: C₂₂H₂₁OP
• 分子量: 332.382
• InChiKey: YSMZAYVFDLZNBM-FGZHOGPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 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-r-oxo-1,2-c,5-t-triphenylphospholane 在 cerium(III) chloride 、 lithium aluminium tetrahydride 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 (+/-)-1,2-c,5-t-triphenylphospholane borane
  参考文献：
  名称：

  Efficient enantiodiscrimination of chiral monophosphine oxides and boranes by phosphorus coupled 13C NMR spectroscopy in the presence of chiral ordering agents

  摘要：

  The synthesis of new chiral phospholanes via the corresponding oxides or boranes is reported and the analytical potential of C-13-{H-1} NMR spectroscopy in weakly ordering polypeptide liquid crystalline phases in view to differentiate between enantiomers of these chiral phosphines precursors is explored. In particular results involving organic solutions of poly-gamma-benzyl-L-glutamate (PBLG) and poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) are described. This NMR approach allows determination of the enantiomeric composition, and provides therefore a new efficient alternative to classical methods usually used to analyze this class of compounds. A description of various spectral enantiodifferentiation patterns expected to be observed using C-13-{H-1} NMR of enantiomers having a spin-1/2 heteroatomic nucleus, embedded in a chiral liquid crystal is presented. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00202-7
• 作为产物：
  描述：

  (+/-)-1-hydroxy-1-oxo-2,5-trans-diphenylphospholane 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 草酰氯 、 1,3-双(二苯基膦)丙烷 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 (+/-)-1-r-oxo-1,2-c,5-t-triphenylphospholane
  参考文献：
  名称：

  通过手性反式-（2,5）-二苯基膦酸的合成和拆分，得到对映体纯的1,2,5-三苯基膦烷

  摘要：

  描述了反式-（2,5）-二苯基膦酸7的合成和拆分。次膦酸7转化为旋光性（1,2,5）-三苯基膦环烷5，在Rh催化N-乙酰基脱氢苯基丙氨酸甲酯加氢反应中用作手性配体，定量得到N-乙酰基苯丙氨酸甲酯的产率为82％ ee

  DOI：

  10.1016/s0040-4039(99)00329-9

文献信息

• Synthesis and first applications of a new family of chiral monophosphine ligand: 2,5-diphenylphosphospholanes
  作者：Frédéric Guillen、Michael Rivard、Martial Toffano、Jean-Yves Legros、Jean-Claude Daran、Jean-Claude Fiaud

  DOI：10.1016/s0040-4020(02)00554-9

  日期：2002.7

  The cyclic phosphinic acid 1-hydroxy-1-r-oxo-2c,5-t-diphenylphospholane was synthesized and resolved into enantiomers through fractional crystallization of the quinine salts. The P-phenyl, P-methyl and P-benzyl tertiary phosphine oxides were obtained from the secondary phosphine oxide, reduction of the oxides afforded the corresponding tertiary P-phenyl and P-benzyl phosphines. Hydrogenation of prochiral

  环状次膦酸1-羟基-1- [R -氧代- 2 Ç，5-吨-diphenylphospholane合成并通过奎宁盐的分级结晶拆分成的对映体。该P -苯基，P -甲基和P -苄基叔膦氧化物从二次膦氧化物得到，还原，得到相应的叔氧化物的P -苯基和P -苄基膦。前手性酰胺的氢化反应用Rh /（S，S）-1-1,2c ，5-叔三苯基膦烷催化体系进行。甲基（Z）-氢化N-乙酰基脱氢肉桂酸酯，得到93％ee的N-乙酰基苯丙氨酸酯。
• Taming Highly Unstable Radical Anions and 1,4-Organodilithiums by Flow Microreactors: Controlled Reductive Dimerization of Styrenes
  作者：Yiyuan Jiang、Hideki Yorimitsu

  DOI：10.1021/jacsau.2c00375

  日期：2022.11.28

  dimerization, and the resulting 1,4-organodilithiums are trapped with various electrophiles. Trapping with divalent electrophiles affords precursors for useful yet less accessible cyclic structures, for example, siloles from dichlorosilanes. Thus, we highlight the power of single-electron reduction of unsaturated compounds in flow microreactors for organic synthesis.

  在流动微反应器中用芳化锂还原苯乙烯导致瞬间产生高度不稳定的自由基阴离子，随后二聚产生相应的 1,4-有机二锂。具有快速混合功能的流动反应器对于这种还原二聚反应至关重要，因为在分批条件下效率和选择性较低。一系列苯乙烯发生二聚反应，生成的 1,4-有机二锂被各种亲电试剂捕获。用二价亲电试剂捕获可提供有用但不易接近的环状结构的前体，例如来自二氯硅烷的噻咯。因此，我们强调了在用于有机合成的流动微反应器中单电子还原不饱和化合物的能力。
• Efficient enantiodiscrimination of chiral monophosphine oxides and boranes by phosphorus coupled 13C NMR spectroscopy in the presence of chiral ordering agents
  作者：Michaël Rivard、Frédéric Guillen、Jean-Claude Fiaud、Christie Aroulanda、Philippe Lesot

  DOI：10.1016/s0957-4166(03)00202-7

  日期：2003.5

  The synthesis of new chiral phospholanes via the corresponding oxides or boranes is reported and the analytical potential of C-13-H-1} NMR spectroscopy in weakly ordering polypeptide liquid crystalline phases in view to differentiate between enantiomers of these chiral phosphines precursors is explored. In particular results involving organic solutions of poly-gamma-benzyl-L-glutamate (PBLG) and poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) are described. This NMR approach allows determination of the enantiomeric composition, and provides therefore a new efficient alternative to classical methods usually used to analyze this class of compounds. A description of various spectral enantiodifferentiation patterns expected to be observed using C-13-H-1} NMR of enantiomers having a spin-1/2 heteroatomic nucleus, embedded in a chiral liquid crystal is presented. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Enantiomerically pure 1,2,5-triphenylphospholane through the synthesis and resolution of the chiral trans-(2,5)-diphenylphospholanic acid
  作者：Frédéric Guillen、Jean-Claude Fiaud

  DOI：10.1016/s0040-4039(99)00329-9

  日期：1999.4

  The synthesis and resolution of trans-(2,5)-diphenylphospholanic acid 7 is described. The phosphinic acid 7 was converted into optically active (1,2,5)-triphenylphospholane 5 which was used as a chiral ligand in Rh-catalyzed hydrogenation of N-acetyl dehydrophenylalanine methyl ester to give quantitative yield of methyl N-acetylphenylalaninate with 82 % e.e.

  描述了反式-（2,5）-二苯基膦酸7的合成和拆分。次膦酸7转化为旋光性（1,2,5）-三苯基膦环烷5，在Rh催化N-乙酰基脱氢苯基丙氨酸甲酯加氢反应中用作手性配体，定量得到N-乙酰基苯丙氨酸甲酯的产率为82％ ee