(-)-(S)-6,6'-bis(diphenylphosphino)[1,1'-biphenyl]-2,2'-diol

• 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: (-)-(S)-6,6'-bis(diphenylphosphino)[1,1'-biphenyl]-2,2'-diol
• 英文别名: (S)-(6,6'-dihydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine)；(S)-OH-BiPhep；3-diphenylphosphanyl-2-(2-diphenylphosphanyl-6-hydroxyphenyl)phenol
• 化学式: C₃₆H₂₈O₂P₂
• 分子量: 554.565
• InChiKey: QCLYZBMPHPUHJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(S)-6,6'-bis(diphenylphosphino)[1,1'-biphenyl]-2,2'-diol 在 二月桂酸二丁基锡 caesium carbonate 作用下， 以 乙腈 为溶剂， 生成 Butyl-carbamic acid 1,13-bis-diphenylphosphanyl-7,8-dihydro-6H-5,9-dioxa-dibenzo[a,c]cyclononen-7-yl ester
  参考文献：
  名称：

  Novel silica gel supported chiral biaryl-diphosphine ligands for enantioselective hydrogenation

  摘要：

  The synthesis of functionalized Biphemp and MeO-Biphep biaryl diphosphine ligands and their covalent attachment to silica gel are described. The catalytic performance of the immobilized ligands was tested in the asymmetric hydrogenation of methyl acetamidocinnamate (MAC) with Rh and of methyl phenylglyoxylate with Ru and compared with that of the homogeneous analogues. With the exception for a Rh catalyzed hydrogenation, where an increase of ee from 29% for the unfunctionalized ligand, to 40% for the functionalized ligand and 45% for the immobilized ligand was observed, functionalization and immobilization did not significantly affect the catalytic properties. The best ees of 90%, were obtained for the Ru catalyzed hydrogenation of methyl phenylglyoxylate with the immobilized MeO-Biphep ligand and are comparable with those of the homogeneous catalyst. Recycling of the immobilized catalysts resulted in a significant drop in activity for the Rh catalysts, whereas the Ru catalysts were much more robust and could be used in >10 catalytic runs. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.05.003
• 作为产物：
  描述：

  (R)-(+)-(6,6′-二甲氧联苯-2,2′-二基)双(二苯基膦) 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到(-)-(S)-6,6'-bis(diphenylphosphino)[1,1'-biphenyl]-2,2'-diol
  参考文献：
  名称：

  杂化手性双轴双膦配体在酮酸酯对映选择性加氢中的匹配和不匹配效应

  摘要：

  高度对映选择性的氢化反应可轻松获得旋光性α-和β-羟基酸衍生物（请参阅方案），这对于合成各种天然产物和具有生物活性的分子而言是非常重要的手性构建基。选择性数据表明，匹配的配体系统为L *，在β-酮酸酯和苯甲酰基甲酸甲酯的氢化反应中具有更高的对映选择性。

  DOI：

  10.1002/chem.200900722
• 作为试剂：
  描述：

  当归内酯 、 色酮 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 2-叔丁基-1,1,3,3-四甲基胍 、 (-)-(S)-6,6'-bis(diphenylphosphino)[1,1'-biphenyl]-2,2'-diol 作用下， 以 2-甲基四氢呋喃 为溶剂， 反应 24.0h， 以98%的产率得到
  参考文献：
  名称：

  将丁烯内酯直接催化不对称和反选择性乙烯基键合到色酮上

  摘要：

  开发了将β，γ-丁烯内酯向色酮的反选择性催化不对称迈克尔型乙烯基加成物。本文开发的催化剂体系的特征在于使用适当的Biphep型手性配体调节空间和电子效应，以转化非对映异构，并通过配位酚醛添加剂改善催化剂的转化率。催化方案使得潜在的具有生物活性的天然产物类似物可以高收率获得，具有适度的非对映选择性和高对映体纯度，大部分大于99％ee。

  DOI：

  10.1039/d0sc01914c

文献信息

• Enantioselective Hydrogenation of β-Ketoesters Using a MeO-PEG-Supported Biphep Ligand under Atmospheric Pressure: A Practical Synthesis of (<i>S</i>)-Fluoxetine
  作者：Quanrui Wang、Liting Chai、Huansheng Chen、Zhiming Li、Fenggang Tao

  DOI：10.1055/s-2006-949650

  日期：2006.9

  The preparation of a novel chiral 2,2′-bis(MeO-PEG-supported)-6,6′-bis(diphenylphosphanyl)biphenyl (MeO-PEG-Biphep) ligand is described. The derived ruthenium complex catalyzes the hydrogenation of β-ketoesters in up to 99% yield and 99% ee under atmospheric pressure. The accelerating effects exerted by the PEG linkage are dramatic when compared to the unsupported analogue, MeO-Biphep-RuBr2. Furthermore, the catalyst can be recovered easily and the recycled catalysts were shown to maintain their efficiency in two consecutive runs, albeit with declining activity. One of the products, (S)-ethyl-3-hydroxy-3-phenylpropanoate, is useful in the preparation of (S)-fluoxetine.

  报道了一种新型手性2,2′-双(甲氧基-PEG-支撑)-6,6′-双(二苯基膦)联苯(MeO-PEG-Biphep)配体的制备。由此衍生的钌配合物在大气压下催化β-酮酯的氢化反应，产率高达99%，对映选择性高达99% ee。与未支撑的类似物MeO-Biphep-RuBr2相比，PEG连接的加速效应显著。此外，该催化剂易于回收，回收的催化剂在连续两次运行中保持其效率，尽管活性有所下降。其中一个产物(S)-乙基-3-羟基-3-苯基丙酸酯在制备(S)-氟西汀中具有应用价值。
• Synthesis of Electronically Deficient Atropisomeric Bisphosphine Ligands and Their Application in Asymmetric Hydrogenation of Quinolines
  作者：Min-Can Wang、Yong-Gui Zhou、De-Yang Zhang、Duo-Sheng Wang、Chang-Bin Yu、Kai Gao

  DOI：10.1055/s-0030-1260129

  日期：2011.9

  atropisomeric bisphos­phine ligands have been synthesized from (S)-MeO-BiPhep. The introduction­ of electron-withdrawing groups in the ligands had a dramatic influence on both the enantioselectivity and the activity of catalyst. The iridium complex of the MeO-BiPhep-based ligand bearing a trifluoromethanesulfonyl group was successfully applied in the asymmetric hydrogenation of quinolines with ee values of up

  从（S）-MeO-BiPhep合成了一系列电子缺陷的阻转异构双膦配体。配体中吸电子基团的引入对催化剂的对映选择性和活性均具有显着影响。具有三氟甲磺酰基的MeO-BiPhep基配体的铱配合物已成功应用于ee值高达95％和周转数（TON）高达14,600的喹啉的不对称氢化中。 铱-不对称氢化-缺电子配体-喹啉
• METHOD FOR SYNTHESIZING OPTICALLY ACTIVE CARBONYL COMPOUNDS
  申请人：BASF SE

  公开号：US20180057437A1

  公开（公告）日：2018-03-01

  The present invention relates to a process for the preparation of an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of at least one optically active transition metal catalyst that is soluble in the reaction mixture and which has rhodium as catalytically active transition metal and a chiral, bidentate bisphosphine ligand, wherein the reaction mixture during the hydrogenation of the prochiral α,β-unsaturated carbonyl compound additionally comprises at least one compound of the general formula (I): in which R 1 , R 2 : are identical or different and are C 6 - to C 10 -aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino; Z is a group CHR 3 R 4 or aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino, wherein R 3 and R 4 are as defined in the claims and the description.

  本发明涉及一种通过在至少一种可溶于反应混合物中的光学活性过渡金属催化剂的存在下，将可溶性光学活性过渡金属铑和手性双膦配体作为催化活性过渡金属的α，β-不对称氢化的可半手性α，β-不饱和羰基化合物与氢气反应制备光学活性羰基化合物的方法。在氢化可半手性α，β-不饱和羰基化合物的过程中，反应混合物中还包括至少一种符合一般式（I）的化合物：其中 R1、R2：相同或不同，为未取代或带有一个或多个（例如1、2、3、4或5个）C6到C10芳基取代基的化合物，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基；Z是一种基团CHR3R4或未取代或带有一个或多个（例如1、2、3、4或5个）取代基的芳基，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基，其中R3和R4如权利要求和说明书中定义。
• Method for the Production of Optically Active Carbonyl
  申请人：Jakel Christoph

  公开号：US20080269528A1

  公开（公告）日：2008-10-30

  The present invention relates to a process for preparing optically active carbonyl compounds by asymmetrically hydrogenating α,β-unsaturated carbonyl compounds in the presence of optically active transition metal catalysts which are soluble in the reaction mixture and have at least one carbon monoxide ligand. The present invention especially relates to a process for preparing optically active aldehydes or ketones, in particular citronellal, by asymmetrically hydrogenating the corresponding optically active α,β-unsaturated aldehydes or ketones.

  本发明涉及一种通过在存在可溶于反应混合物中并具有至少一个一氧化碳配体的光学活性过渡金属催化剂的情况下，对α，β-不饱和羰基化合物进行不对称氢化的方法。本发明特别涉及一种通过对相应的光学活性α，β-不饱和醛或酮进行不对称氢化而制备光学活性醛或酮的方法，特别是柠檬醛。
• Photomechanical Actuation of Ligand Geometry in Enantioselective Catalysis
  作者：Zachary S. Kean、Sergey Akbulatov、Yancong Tian、Ross A. Widenhoefer、Roman Boulatov、Stephen L. Craig

  DOI：10.1002/anie.201407494

  日期：2014.12.22

  A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity

  报道了一种将光开关偶联到手性双（膦）配体的联芳基主链上的催化剂，从而允许对配体的几何形状进行光化学操作而不会干扰电子结构。转换时催化剂活性和选择性的变化可归因于分子内的机械力，从而为新型催化剂奠定了基础，其选择性可通过控制催化剂在周转过程中所经历的分子应力而在合适的范围内平稳地就地变化。 。产生的力约为100 pN，因此导致不对称的Heck芳基化和Trost烯丙基烷基化的对映选择性的可测量变化。