(4S,5S)-5-methyl-2-phenyl-4-[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropan-2-yl]-4,5-dihydro-1,3-oxazole | 1040384-59-5

• 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: (4S,5S)-5-methyl-2-phenyl-4-[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropan-2-yl]-4,5-dihydro-1,3-oxazole
• CAS: 1040384-59-5
• 化学式: C₄₁H₅₆NO₄P
• 分子量: 657.874
• InChiKey: DAPLGYMOPLFEEC-LHAPQZOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.4
• 重原子数：
  47
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  57.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 (4S,5S)-5-methyl-2-phenyl-4-[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropan-2-yl]-4,5-dihydro-1,3-oxazole 、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 二氯甲烷 、 水 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Iridium Phosphite−Oxazoline Catalysts for the Highly Enantioselective Hydrogenation of Terminal Alkenes

  摘要：

  A modular library of readily available phosphite-oxazoline ligands (L1-L16a-f) has been successfully applied for the first time in the Ir-catalyzed asymmetric hydrogenation of a broad range of highly unfunctionalized 1,1,-disubstituted terminal alkenes. Enantioselectivities up to >99% and full conversions were obtained in several 1, 1 -disubstituted alkenes, including substrate classes that have never been asymmetrically hydrogenated before (i.e,, 1,1-heteoraryl-alkyl, 1,1-diaryl, trifluoromethyl, etc.). The results indicated that these catalytic systems have high tolerance to the steric and electronic requirements of the substrate and also to the presence of a neighboring polar group. The asymmetric hydrogenations were also performed using propylene carbonate as solvent, which allowed the It catalyst to be reused and maintained the excellent enantioselectivities.

  DOI：

  10.1021/ja904152r
• 作为产物：
  描述：

  3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl phosphorochloridite 、 在 吡啶 作用下， 以 甲苯 为溶剂， 以77%的产率得到(4S,5S)-5-methyl-2-phenyl-4-[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropan-2-yl]-4,5-dihydro-1,3-oxazole
  参考文献：
  名称：

  用于不对称钯催化的烯丙基取代反应的模块化亚磷酸酯-恶唑啉/恶嗪配体库：对映选择性的范围和局限性。

  摘要：

  已合成了亚磷酸酯-恶唑啉/恶嗪配体L1-L15ah的文库，并在Pd催化的几种底物类型的烯丙基取代反应中进行了筛选。这些系列的配体可以由容易获得的羟基氨基酸衍生物有效地制备。它们的模块性质使恶唑啉/恶嗪部分，烷基主链和亚磷酸二芳基酯部分中的取代基/构型易于系统地变化。因此，通过仔细选择配体组分，在广泛的单和双取代线性受阻和不受阻衬板和环状底物范围内，获得了很高的区域和对映选择性（ee值高达99％）和良好的活性。对Pd-pi-烯丙基中间体的NMR研究提供了对配体参数对对映选择性起源的影响的更深刻的理解。这也表明亲核攻击主要发生在反式为亚磷酸酯部分的烯丙基末端碳原子上。

  DOI：

  10.1002/chem.200701636

文献信息

• Iridium Phosphite−Oxazoline Catalysts for the Highly Enantioselective Hydrogenation of Terminal Alkenes
  作者：Javier Mazuela、J. Johan Verendel、Mercedes Coll、Benjamín Schäffner、Armin Börner、Pher G. Andersson、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1021/ja904152r

  日期：2009.9.2

  A modular library of readily available phosphite-oxazoline ligands (L1-L16a-f) has been successfully applied for the first time in the Ir-catalyzed asymmetric hydrogenation of a broad range of highly unfunctionalized 1,1,-disubstituted terminal alkenes. Enantioselectivities up to >99% and full conversions were obtained in several 1, 1 -disubstituted alkenes, including substrate classes that have never been asymmetrically hydrogenated before (i.e,, 1,1-heteoraryl-alkyl, 1,1-diaryl, trifluoromethyl, etc.). The results indicated that these catalytic systems have high tolerance to the steric and electronic requirements of the substrate and also to the presence of a neighboring polar group. The asymmetric hydrogenations were also performed using propylene carbonate as solvent, which allowed the It catalyst to be reused and maintained the excellent enantioselectivities.
• Modular Phosphite–Oxazoline/Oxazine Ligand Library for Asymmetric Pd-Catalyzed Allylic Substitution Reactions: Scope and Limitations—Origin of Enantioselectivity
  作者：Montserrat Diéguez、Oscar Pàmies

  DOI：10.1002/chem.200701636

  日期：2008.4.18

  A library of phosphite-oxazoline/oxazine ligands L1-L15 a-h has been synthesized and screened in the Pd-catalyzed allylic substitution reactions of several substrate types. These series of ligands can be prepared efficiently from easily accessible hydroxyl amino acid derivatives. Their modular nature enables the substituents/configurations in the oxazoline/oxazine moiety, alkyl backbone chain and in

  已合成了亚磷酸酯-恶唑啉/恶嗪配体L1-L15ah的文库，并在Pd催化的几种底物类型的烯丙基取代反应中进行了筛选。这些系列的配体可以由容易获得的羟基氨基酸衍生物有效地制备。它们的模块性质使恶唑啉/恶嗪部分，烷基主链和亚磷酸二芳基酯部分中的取代基/构型易于系统地变化。因此，通过仔细选择配体组分，在广泛的单和双取代线性受阻和不受阻衬板和环状底物范围内，获得了很高的区域和对映选择性（ee值高达99％）和良好的活性。对Pd-pi-烯丙基中间体的NMR研究提供了对配体参数对对映选择性起源的影响的更深刻的理解。这也表明亲核攻击主要发生在反式为亚磷酸酯部分的烯丙基末端碳原子上。