Alkali‐Phosphorverbindungen und ihr reaktives Verhalten, LIX. Synthese und Reaktionsverhalten der 2‐Amino‐äthylphosphine

Abstract

NaPH2 reagiert in flüss. Ammoniak mit 2‐Chlor‐äthylaminen zu 2‐Amino‐äthylphosphinen H2PCH2CH2NRR′(13), die als PH‐acide Substanzen nach erneuter Metallierung und Kupplung mit Alkylhalogeniden zu R′′P(H)CH2CH2NRR (4 – 10) und mit Dihalogenalkanen zu [CH2]n(P(H)CH2CH2NR2)2 (13 – 16) führen. Analog lassen sich ausgehend von C6H5PH2 oder 1 und 3 mit 2‐Chlor‐äthylaminen C6H5P(H)CH2CH2NRR′ und Bis‐ bzw. Tris‐[2‐amino‐äthyl]‐phosphine (17–21) gewinnen. Die Oxydation sek. 2‐Aminoäthylphosphine mit Schwefel liefert [2‐Amino‐äthyl]‐alky‐ bzw. ‐aryldithiophosphinsäuren (22–26) mit Zwitterionenstruktur. Durch gleichzeitige Einwirkung von Diäthylamin und Formaldehyd auf PH‐funktionelle 2‐Amino‐äthylphosphine entstehen [(C2H5)2NCH2]nP‐[CH2CH2NR2]3–n (27, 28).

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: New Mechanistic Insights Using D2O as Deuterium‐Labeling Agent

“…1 3 }], were prepared according to the literature. [11,15,44,45] The preparation of the optically pure version of the latter ligand, (S,S)-1, has been previously reported [11] The synthesis of complex [RhCl(COD)(α-P,N)] 1 with α-P,N=Ph 2 PCH(o-C 6 H 4 Cl[Cr(CO) 3 ])NHPh has previously been described. [17] The (R)-2-phenylpropanal was prepared by an oxidation reaction using the Dess-Martin reagent [46] from commercially available (R)-2-phenyl-1-propanol (Aldrich) according to a previously described procedure [47] (ee = 93 % by use of the NMR chiral shift reagent [Eu(hfc) 3 ], according to the literature [48] ).…”

Amino‐phosphanes in RhI‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

“…The coordinated 1,5-COD (1,5-cyclooctadiene) C and H nuclei are labeled from 1 to 8, C 1 and C 2 being trans to P. ) (γ-P,N-1), and Ph 2 P(o-C 6 H 4 -CH 2 NHPh) (γ-P,N-2) were prepared according to literature. [13,14,17,[41][42][43][44] The synthesis of complex [RhCl(COD)(α-P,N)] 1 with α-P,N=Ph 2 PCH(o-C 6 H 4 Cl[Cr(CO) 3 ])NHPh has previously been described. [18] …”

Synthesis, Coordination to Rh(I), and Hydroformylation Catalysis of New β-Aminophosphines Bearing a Dangling Nitrogen Group: An Unusual Inversion of a Rh-Coordinated P Center

“…Aminophosphine ligands are being intensively investigated because of the catalytic applications of their corresponding Ru, 1,2 Ni, 3,4 Rh [5][6][7][8] and Pd [9][10][11] complexes. Although the preparation of chiral versions of -P,N ligands requires in general tedious multistep procedures, [12][13][14][15] some have been shown to be efficient in asymmetric enantioselective allylic alkylations, 16 hydroformylation 7 and hydrogenation. 12 We have recently reported a novel and relatively simple synthetic procedure for the preparation of chiral -aminophosphines, which consists of the nucleophilic addition of a phosphinomethyl carbanion onto an imine.…”