(R,R)-1-chloro-2,5-dimethylphospholane | 936836-94-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: (R,R)-1-chloro-2,5-dimethylphospholane
• 英文别名: (2R,5R)-1-chloro-2,5-dimethylphospholane
• CAS: 936836-94-1
• 化学式: C₆H₁₂ClP
• 分子量: 150.588
• InChiKey: QNSAVUYBQOYBIA-PHDIDXHHSA-N

物化性质

• 沸点：
  100-105 °C(Press: 75.0 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (R,R)-1-chloro-2,5-dimethylphospholane 在 正丁基锂 、 甲酸 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.67h， 生成 (2R,5R)-2,5-dimethyl-1-(1'-oxo-1',2'-dihydro-isoquinolin-3'-yl)-phospholane
  参考文献：
  名称：

  自组装和非组装单齿膦配体的对映选择性钯催化的烯丙基胺化

  摘要：

  通过将溴取代的杂环与对映纯的结构单元（2 R，5 R）-2,5-二甲基-1-氯膦烷偶联制备新的手性膦酸酯。一些新的膦配体具有通过金属络合物中的氢键自组装的潜力。通过在钯催化的烯丙基胺化反应中应用这些和相关的配体，可以实现高对映选择性（最高99％）。分析了环状膦配体的构造对对映选择性的影响。

  DOI：

  10.1016/j.tetasy.2007.08.026
• 作为产物：
  描述：

  (R,R)-2,5-dimethyl-1-(trimethylsilyl)phospholane 在 六氯乙烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以93%的产率得到(R,R)-1-chloro-2,5-dimethylphospholane
  参考文献：
  名称：

  手性对氯膦烷：用于合成配体的多功能构件

  摘要：

  描述了对映体纯 (R,R)-1-氯-2,5-二甲基磷烷的合成，其可用于合成各种带有磷烷部分的膦配体。

  DOI：

  10.1055/s-2007-967974

文献信息

• Efficient Enantioselective Synthesis of Optically Active Diols by Asymmetric Hydrogenation with Modular Chiral Metal Catalysts
  作者：Renat Kadyrov、René M. Koenigs、Claus Brinkmann、David Voigtlaender、Magnus Rueping

  DOI：10.1002/anie.200902835

  日期：2009.9.28

  Valuable vicinal 1,2‐diols can be prepared with high enantioselectivity by the asymmetric ruthenium‐catalyzed hydrogenation of aryl‐ and alkyl‐substituted α‐hydroxy ketones (see scheme). The ligands, which are distinguished by their modular construction, display excellent enantioface differentiation.

  通过不对称钌催化的芳基和烷基取代的α-羟基酮的不对称氢化，可以制备高价的邻位1,2-二醇（参见方案）。配体以其模块化结构而著称，表现出出色的对映体分化。
• Distinct Reactivity of Mono- and Bis-NHC Silver Complexes: Carbene Donors versus Carbene–Halide Exchange Reagents
  作者：Ulrich Hintermair、Ulli Englert、Walter Leitner

  DOI：10.1021/om101056y

  日期：2011.7.25

  N-heterocyclic carbene (NHC) complexes of silver is an established technique for their use as carbene transfer reagents. While it is known that both mono-NHC Ag(I) and bis-NHC Ag(I) complexes are accessible, different reactivities of these species have not been explored synthetically. Whereas the commonly used mono-NHC Ag(I) complexes act as NHC donors only, we found that a bis-NHC Ag(I) complex was capable of transferring

  银的N-杂环卡宾（NHC）配合物的合成是一种成熟的技术，可用作它们的卡宾转移试剂。虽然已知单-NHC Ag（I）和双-NHC Ag（I）配合物均可使用，但尚未对这些物质的不同反应性进行合成研究。尽管常用的单-NHC Ag（I）配合物仅充当NHC供体，但我们发现双-NHC Ag（I）配合物能够在卤化物抽象下转移一种卡宾。这可以通过bis-NHC Ag（I）配合物而不是其相应的mono-NHC Ag（I）配合物将P-Cl化合物转化为相应的咪唑鎓-膦来举例说明。当双-NHC Ag（I）配合物与[M（cod）Cl] 2反应时（M = Rh，Ir），两个NHC均在氯化物提取下转移，仅得到[M（cod）（NHC）2 ] +，据报道该反应甚至在[M（cod）Cl（NHC）]处停止。在AgPF 6存在下过量的单-NHC Ag（I）配合物。
• Synthesis of Binol-based diphosphinites bearing chiral phospholane units and their application in asymmetric catalysis
  作者：Tim Hammerer、Laurent Weisgerber、Stefan Schenk、Othmar Stelzer、Ulli Englert、Walter Leitner、Giancarlo Franciò

  DOI：10.1016/j.tetasy.2011.12.011

  日期：2012.1

  New diphosphinite ligands based on atropoisomeric diol backbones and (R,R)-2,5-dimethylphospholane moieties have been prepared and fully characterised. For each ligand structure, both diastereomers have been synthesised. These ligands are available through a straightforward procedure in good yields. The solid state structures of two diastereomeric ligands are reported. These ligands have been applied to Rh-catalysed asymmetric hydrogenations and hydroformylations of C=C bonds as well as in Ir-catalysed asymmetric hydrogenations of C=N bonds. Turnover frequencies in the range of 10,000 h(-1) and enantioselectivities of up to 98% ee have been achieved. The different chirality elements within the ligands led to marked cooperative effect in catalysis. Interestingly, there is no general privileged diastereomeric structure but rather a matched diastereomer for each application. (C) 2012 Elsevier Ltd. All rights reserved.
• Asymmetric Rhodium(I)-Catalyzed C–C Activations with Zwitterionic Bis-phospholane Ligands
  作者：Evelyne Parker、Nicolai Cramer

  DOI：10.1021/om4011627

  日期：2014.2.10

  The development of unconventional ligand scaffolds is an important aspect to alter reaction pathways of transition-metal-catalyzed reactions. The nature of the counterion of cationic metal complexes plays an important role in the catalyst reactivity. We herein report a chiral anionic bidentate bis-phosphine ligand based on the popular phospholane scaffold. Subsequently, zwitterionic rhodium(I) complexes with no external counterion were synthesized, and their potential was evaluated in asymmetric carbon carbon bond activation of cyclobutanones. This type of rhodium complex allows, for a significantly lower reaction temperature than analogous cationic rhodium complexes and enables, for the first time, asymmetric transformations with up to 93.5:6.5 enantiomeric ratio.
• Synthesis of Josiphos-Type Bisphospholane Ligands
  作者：Giancarlo Franciò、Walter Leitner、Tim Hammerer、Andrea Dämbkes、Wolfgang Braun、Albrecht Salzer

  DOI：10.1055/s-0032-1316755

  日期：2012.9

  Bisphospholane Josiphos-type ligands were synthesized in high yields employing electrophilic and nucleophilic phospholane synthons. Full characterization data including solid-state structures of the diastereomeric ligands are reported. These ligands resulted in active and enantioselective iridium catalysts for the asymmetric hydrogenation of imines. Pronounced cooperative effects of the chiral elements within the ligand structure were observed and enantioselectivities of up to 74% ee were achieved.