1636-15-3Relevant articles and documents
Copper(I)-Catalyzed Asymmetric Synthesis of P-Chiral Aminophosphinites
Li, Yan-Bo,Tian, Hu,Xiao, Jun-Zhao,Yin, Liang,Zhang, Shuai
supporting information, (2022/02/17)
Herein, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines is developed. In the cases of symmetrical diarylphosphines, a series of aminophosphinites is prepared in high yields. In the cases of unsymmetrical diarylphosphines, an array of P-chiral aminophosphinites is synthesized in high yields with high enantioselectivity by using a copper(I)-(R,RP)-Ph-FOXAP complex as a chiral catalyst. Based on several control experiments and 31P NMR studies, a two-electron redox mechanism involving the dynamic kinetic asymmetric transformation of unsymmetrical diarylphosphines is proposed for the copper(I)-catalyzed asymmetric reaction. Finally, one representative P-chiral phosphoric amide generated through the oxidation with H2O2 is transformed to a chiral diarylphosphinate in high yield with retained enantioselectivity, which allows further transformations towards various P-chiral tertiary phosphines.
Phosphino-amine (PN) Ligands for Rapid Catalyst Discovery in Ruthenium-Catalyzed Hydrogen-Borrowing Alkylation of Anilines: A Proof of Principle
Broomfield, Lewis Marc,Wu, Yichen,Martin, Eddy,Shafir, Alexandr
supporting information, p. 3538 - 3548 (2016/01/25)
A general synthetic protocol for the synthesis of simple phosphino-amine (PN) ligands is described with 19 ligands being isolated in good yields. High-throughput ligand screening uncovered the success of two of these ligands for aromatic amine alkylations via ruthenium-catalyzed hydrogen borrowing reactions. The combination of N,N'-bis(diphenylphosphino)-N,N′-dimethylpropylenediamine with a ruthenium(II) source and potassium hydroxide (15 mol%) is the optimal system for selective monobenzylations of aromatic amines (method A). Over 70% isolated yields have been achieved for the formation of 14 secondary aromatic amines under mild reaction conditions (120 C and 1.05 equivalents of benzyl alcohol). On the other hand, N,N-bis(diphenylphosphino)-isopropylamine was the ligand utilized for both selective monomethylation and monoethylation reactions of aromatic amines (method B). Here the alcohol is charged as both the reaction medium and substrate and 9 examples are disclosed with all isolated yields exceeding 70%. These methods have been applied to the synthesis of important synthetic building blocks based on aminoferrocene.
Cleavage of P=O in the presence of P-N: Aminophosphine oxide reduction with in situ boronation of the PIII product
Kenny, Niall P.,Rajendran, Kamalraj V.,Jennings, Elizabeth V.,Gilheany, Declan G.
supporting information, p. 14210 - 14214 (2013/11/06)
In contrast to tertiary phos-phine oxides, the deoxygenation of aminophosphine oxides is effectively impossible due to the need to break the immensely strong and inert P=O bond in the presence of a relatively weak and more reactive P-N bond. This long-sta
