N-(1-thiophen-3-ylethylidene)diphenylphosphinamide

• 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: N-(1-thiophen-3-ylethylidene)diphenylphosphinamide
• 英文别名: N-[(E)-1-(3-thienyl)ethylidene]diphenylphosphinic amide；(E)-N-diphenylphosphoryl-1-thiophen-3-ylethanimine
• 化学式: C₁₈H₁₆NOPS
• 分子量: 325.371
• InChiKey: ZFESHNJGNJAGCZ-XDJHFCHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(1-thiophen-3-ylethylidene)diphenylphosphinamide 在 [ReOCl3(OPPh3)(SMe2)] 、 (R,R)-bis[4-(4-t-Bu-Phe)-4,5-dihydrooxazol-2-yl]acetonitrile 、 二甲基苯基硅烷 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到P,P-Diphenyl-N-[(1R)-1-(3-thienyl)ethyl]phosphinic amide
  参考文献：
  名称：

  Enantioselective Reduction of Imines Catalyzed by a Rhenium(V)−Oxo Complex

  摘要：

  An air- and moisture-tolerant enantioselective hydrosilylation of N-phosphinyl imines employing a chiral Re(V)-oxo complex as a catalyst is described. The chiral catalyst is a cyanobis(oxazoline) (CNbox)-ligated rhenium-oxo complex of the general formula (CNbox)Re(O)Cl2(OPPh3). Using this catalyst, a wide range of aromatic imines (including cyclic, acyclic, and heteroaromatic), alpha-iminoesters, and alpha,beta-unsaturated imines are reduced with good to excellent enantioselectivities.

  DOI：

  10.1021/ja050831a
• 作为产物：
  描述：

  3-acetylthiophene oxime 、 二苯基次膦酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以61%的产率得到N-(1-thiophen-3-ylethylidene)diphenylphosphinamide
  参考文献：
  名称：

  Enantioselective Reduction of Imines Catalyzed by a Rhenium(V)−Oxo Complex

  摘要：

  An air- and moisture-tolerant enantioselective hydrosilylation of N-phosphinyl imines employing a chiral Re(V)-oxo complex as a catalyst is described. The chiral catalyst is a cyanobis(oxazoline) (CNbox)-ligated rhenium-oxo complex of the general formula (CNbox)Re(O)Cl2(OPPh3). Using this catalyst, a wide range of aromatic imines (including cyclic, acyclic, and heteroaromatic), alpha-iminoesters, and alpha,beta-unsaturated imines are reduced with good to excellent enantioselectivities.

  DOI：

  10.1021/ja050831a

文献信息

• Catalytic enantioselective Strecker reaction of ketoimines using catalytic amount of TMSCN and stoichiometric amount of HCN
  作者：Nobuki Kato、Masato Suzuki、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tetlet.2004.02.077

  日期：2004.4

  Catalyst loading as low as 0.1 mol % was achieved in the enantioselective Strecker reaction of ketoimines. Excellent enantioselectivity was obtained with a combined use of a catalytic amount of TMSCN and a stoichiometric amount of HCN as a reagent, and a chiral gadolinium complex as a catalyst.

  在酮亚胺的对映选择性斯特雷克反应中，催化剂的负载量低至0.1摩尔％。结合使用催化量的TMSCN和化学计算量的HCN作为试剂，以及手性g络合物作为催化剂，可获得出色的对映选择性。
• Assembly State of Catalytic Modules as Chiral Switches in Asymmetric Strecker Amino Acid Synthesis
  作者：Nobuki Kato、Tsuyoshi Mita、Motomu Kanai、Bruno Therrien、Masaki Kawano、Kentaro Yamaguchi、Hiroshi Danjo、Yoshihisa Sei、Akihiro Sato、Sanae Furusho、Masakatsu Shibasaki

  DOI：10.1021/ja060841r

  日期：2006.5.1

  demonstrate novel properties as asymmetric catalysts. We report the three-dimensional structures of two such asymmetric catalysts (crystals A and B) for Strecker alpha,alpha-disubstituted amino acid synthesis. These complexes are constructed via assembly of the same chiral modules derived from d-glucose, but their assembly modes differ. The enantioselectivity in the Strecker reaction was dramatically switched

  自组装手性多金属配合物通常表现出作为不对称催化剂的新特性。我们报告了用于 Strecker α、α-二取代氨基酸合成的两种这种不对称催化剂（晶体 A 和 B）的三维结构。这些复合物是通过组装来自 d-葡萄糖的相同手性模块构建的，但它们的组装模式不同。Strecker 反应中的对映选择性发生了显着变化，具体取决于使用的组装模式：原位生成的催化剂，其结构由晶体 B 或晶体 A 表示。这些发现提供了对高阶结构的功能重要性的洞察一种人工催化剂。
• Enantioselective Strecker-type reaction of phosphinoyl ketimines catalyzed by a chiral Zr-bipyridyldiol catalyst
  作者：Yi-Jing Chen、Chinpiao Chen

  DOI：10.1016/j.tetasy.2008.09.011

  日期：2008.9

  An enantioselective Strecker reaction of N-diphenylphosphinoyl ketimines with TMSCN employing a chiral zirconium complex formed from chiral bipyridyl diol 1 as catalyst is described. The catalytic efficiency of chiral ligand 1 with other Lewis acids was also explored. Higher yields (50-85%) with moderate to good enantioselectivities (30-80%) were achieved for a variety of N-diphenylphosphinoyl ketimines. (C) 2008 Elsevier Ltd. All rights reserved.
• General and practical catalytic enantioselective Strecker reaction of ketoimines: significant improvement through catalyst tuning by protic additives
  作者：Nobuki Kato、Masato Suzuki、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tetlet.2004.02.082

  日期：2004.4

  Significant improvement in enantioselectivity and catalyst activity was achieved for the catalytic enantio selective Strecker reaction. Using a catalyst (1-2.5 mol%) prepared from Gd((OPr)-Pr-i)(3) and D-glucose derived ligand 1, and in the presence of 2,6-dimethylphenol as an additive, high enantioselectivity was obtained from a wide range of ketoimines, including heteroaromatic and cyclic ketoimines. The new method was applied to an efficient catalytic asymmetric synthesis of sorbinil, a therapeutic agent for diabetic complications. (C) 2004 Elsevier Ltd. All rights reserved.
• Enantioselective Reduction of Imines Catalyzed by a Rhenium(V)−Oxo Complex
  作者：Kristine A. Nolin、Richard W. Ahn、F. Dean Toste

  DOI：10.1021/ja050831a

  日期：2005.9.1

  An air- and moisture-tolerant enantioselective hydrosilylation of N-phosphinyl imines employing a chiral Re(V)-oxo complex as a catalyst is described. The chiral catalyst is a cyanobis(oxazoline) (CNbox)-ligated rhenium-oxo complex of the general formula (CNbox)Re(O)Cl2(OPPh3). Using this catalyst, a wide range of aromatic imines (including cyclic, acyclic, and heteroaromatic), alpha-iminoesters, and alpha,beta-unsaturated imines are reduced with good to excellent enantioselectivities.