(2S,5S)-(-)-1-chloro-1-oxo-2,5-diphenylphospholane | 474093-56-6

• 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: (2S,5S)-(-)-1-chloro-1-oxo-2,5-diphenylphospholane
• 英文别名: (S,S)-(-)-1-chloro-1-r-oxo-2-c,5-t-diphenylphospholane；(2S,5S)-1-chloro-2,5-diphenyl-1lambda5-phospholane 1-oxide；(2S,5S)-1-chloro-2,5-diphenyl-1λ5-phospholane 1-oxide
• CAS: 474093-56-6
• 化学式: C₁₆H₁₆ClOP
• 分子量: 290.729
• InChiKey: ZYPZZVAKMUOKCV-HOTGVXAUSA-N

物化性质

• 熔点：
  133-136 °C
• 沸点：
  484.9±45.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  (2S,5S)-(-)-1-chloro-1-oxo-2,5-diphenylphospholane 在 氨 、 氢溴酸 、 四氯化钛 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 30.75h， 生成 (S,S)-1-hydroxy-1-oxo-2,5-trans-diphenylphospholane
  参考文献：
  名称：

  N-Phosphinyl Imine Chemistry (I): Design and Synthesis of Novel N-Phosphinyl Imines and their Application to Asymmetric aza-Henry Reaction

  摘要：

  Novel chiral N‐phosphinamide and N‐phosphinyl imines have been designed, synthesized and applied to asymmetric aza‐Henry reaction to give excellent chemical yields (92%– quant.) and diastereoselectivity (91% to >99%de). The reaction showed a great substrate scope in which aromatic/aliphatic aldehyde‐ and ketone‐derived N‐phosphinyl imines can be employed as electrophiles. The chiral N‐phosphinamide can be stored at room temperature for more than 2 months without inert gas protection, and chiral N‐phosphinyl imines were also proven to be highly stable at room temperature for a long period under inert gas protection. The N‐phosphinyl group enabled the product purification to be performed simply by washing crude product with EtOAc and hexane. This reaction joined other eight GAP (Group‐Assistant‐Purification) chemistry processes that were developed in our laboratories. The absolute configuration has been unambiguously determined by converting a β‐nitroamine product into a known N‐Boc sample.

  DOI：

  10.1111/j.1747-0285.2010.01047.x
• 作为产物：
  描述：

  1,4-二苯基-1,3丁二烯 在 palladium on activated charcoal 三氯化铝 、 草酰氯 、 氢气 、 sodium methylate 、 奎宁 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 20.0 ℃ 、5.0 MPa 条件下， 反应 2.08h， 生成 (2S,5S)-(-)-1-chloro-1-oxo-2,5-diphenylphospholane
  参考文献：
  名称：

  自组装铑膦烷催化剂的对映选择性氢化：配体结构和溶剂的影响。

  摘要：

  已经制备了三组新的和相关的手性磷杂环戊烯和磷脂碱配体用于Rh催化的对映选择性氢化。环状单膦的大小和取代方式是变化的。更重要的是，配体在与三价磷原子连接的杂环基团的性质上有所不同：2-吡啶酮或2-烷氧基吡啶。在相应的Rh络合物中，两个单齿P配体的吡啶酮单元可通过氢键组装并形成螯合物。相反，带有烷氧基吡啶附属物的合成前体不能通过分子内氢键聚集。自组装的性质取决于P配体的性质和用于氢化的溶剂（CH2Cl2对MeOH）。这些特征会影响反应速度以及对映选择性，

  DOI：

  10.1002/chem.200601607

文献信息

• Synthesis of Enantiopure 1-r-Alkyl-2-c,5-t-Diphenylphospholanes and Phospholanium Salts through Direct Alkylation of Phospholane
  作者：Cristian Dobrota、Amelie Duraud、Martial Toffano、Jean-Claude Fiaud

  DOI：10.1002/ejoc.200800070

  日期：2008.5

  Chiral enantiopure 1-alkyl-2,5-diphenylphospholanium salts were obtained in one step through alkylation of phospholane with alkyl triflates. The resulting air-stable phosphonium salts are electron-rich trialkylphosphane precursor ligands for transition metals, and they offer a convenient route toward chiral quaternary phosphonium salts as phase-transfer agents.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451

  手性对映体纯 1-烷基-2,5-二苯基磷鎓盐通过磷烷与烷基三氟甲磺酸酯的烷基化一步获得。所得的空气稳定鏻盐是过渡金属的富电子三烷基膦前体配体，它们为手性季鏻盐作为相转移剂提供了方便的途径。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2008）
• 1-Alkoxy-2,5-diphenylphospholane and -phospholanium Salts in Rhodium-Catalyzed Asymmetric Hydrogenation
  作者：Aurore Galland、Jean Marc Paris、Thierry Schlama、Régis Guillot、Jean-Claude Fiaud、Martial Toffano

  DOI：10.1002/ejoc.200600884

  日期：2007.2

  A series of chiral enantiopure phosphinites was synthesized in four steps starting from phosphinic acid. New species were obtained as alkoxyphosphonium compounds. They can be used in the asymmetric hydrogenation of functionalized alkenes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  以次膦酸为原料，分四步合成了一系列手性对映纯次膦酸酯。获得了作为烷氧基鏻化合物的新物种。它们可用于官能化烯烃的不对称氢化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Enantioselective Synthesis of Atropisomeric Biaryls using Biaryl 2,5‐Diphenylphospholanes as Ligands for Palladium‐Catalysed Suzuki‐Miyaura Reactions
  作者：Liam Byrne、Christian Sköld、Per‐Ola Norrby、Rachel H. Munday、Andrew R. Turner、Peter D. Smith

  DOI：10.1002/adsc.202001211

  日期：2021.1.5

  describe the development of biaryl 2,5‐diphenylphospholanes as a new class of C2‐symmetric, monodentate ligands for asymmetric Suzuki‐Miyaura (ASM) reactions. Screening of a series of exemplary phospholanes led to the identification of two ligands that were used to prepare a range of atropisomeric biaryl and heterobiaryl products with good to excellent levels of enantioselectivity (up to 97:3 e.r.) under

  在这里，我们将联芳基2,5-二苯基膦酸酯的开发描述为用于不对称铃木-宫浦（ASM）反应的一类新的C 2对称单齿配体。一系列示例性膦酸酯的筛选导致鉴定了两个配体，这些配体用于在温和条件下制备对映异构性联芳基和杂联二芳基产品，对映选择性好至极好（至高97：3 er）。DFT研究表明，约束配位体的形成以及优化配体中的联芳基甲氧基中的一个与金属中心的配位对于限制键形成步骤中的构象自由度至关重要。
• Bis-(2,5-diphenylphospholanes) with sp² Carbon Linkers:  Synthesis and Application in Asymmetric Hydrogenation
  作者：Martin E. Fox、Mark Jackson、Ian C. Lennon、Jerzy Klosin、Khalil A. Abboud

  DOI：10.1021/jo7014938

  日期：2008.2.1

  chiral diphosphine ligands consisting of bis(2,5-diphenylphospholan-1-yl) groups connected by the sp2 carbon linkers 2,3-quinoxaline ((S,S)-Ph-Quinox), 2,3-pyrazine ((S,S)-Ph-Pyrazine), maleic anhydride ((S,S)-Ph-MalPhos), and 1,1‘-ferrocene ((S,S)-Ph-5-Fc) were synthesized, and their cationic [rhodium(I)(COD)] complexes were prepared. These complexes were tested in asymmetric hydrogenation of functionalized

  四个由双（2,5-二苯基膦基-1-基）基团组成的手性二膦配体，它们通过sp 2碳连接基2,3,3-喹喔啉（（S，S）-Ph-Quinox），2,3-吡嗪（（小号，小号）-Ph -吡嗪），马来酸酐（（小号，小号）-Ph-MalPhos），和1,1'-二茂铁（（小号，小号）-Ph-5-FC）的合成，和它们的阳离子制备[铑（I）（COD）]配合物。这些配合物在官能化烯烃的不对称氢化中进行了测试。[（（S，S）-Ph-Quinox）Rh（COD）] BF 4表现出对衣康酸酯和脱氢氨基酸底物的高活性和选择性。相应的（S，S）-Ph-吡嗪和（S，S）-Ph-MalPhos配合物表现出较低的活性和选择性。[[（（S，S）-Ph-5-Fc）Rh（COD）] BF 4对这些底物表现出高活性且选择性低，但对2-C取代肉桂酸酯盐却具有高活性和选择性，而（S，S）-Ph-Quinox和（R，R）-Ph-BPE对2
• 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。