Aminophosphines synthesis

Benito-Garagorri D, Kirchner K (2(X)8) Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines synthesis and catalytic applications. Acc Chem Res 41 201-213... 

A method for the synthesis of long-chain aminophosphinic acids having surface-active and antibacterial activity followed the procedure developed by Schmidt [182]. It is based on the condensation of the hypophosphite salt of a primary amine with an aldehyde or ketone [183], as shown in Eq. (108) ... 

Agbossou E., Carpentier J. E. Hapiot E., Suisse I., Mortreux A. The Aminophos-phine-Phosphinites and Related Ligands Synthesis, Coordination Chemistry and Enantioselective Catalysis Coord. Chem. Rev. 1998 I78-I80 1615-1645 Keywords stereoselective Diels-Alder reaction catalysts, aminophosphine-phosphinites, enantioselective catalysts... 

Polymer supported xanthene derivatives have been used in the solid phase synthesis of 1-aminophosphinic acids, RCH(NH2)PH(0)0H, <%TL1647> and of C-terminal peptide amides <96JOC6326>. Xanthene units also feature in crown ethers <96JCS(P2)2091>, calixarenes <96JOC5670> and in a flexible template for a P-sheet nucleator <96JOC7408>. 

Other chiral ligands such as BINAP (where BINAP is bis(diarylphosphino)-1,1 binaphthyl) or aminophosphines are also efficient for stereoselective synthesis of chiral-at-metal Ru complexes [39-41]. 

Campbell, M.M. and Carruthers, N., Synthesis of a-aminophosphonic and a-aminophosphinic acids and derived dipeptides from 4-acetoxyazetidin-2-ones, Chem. Commun., 730, 1980. 

Scheme 33.4 One-step synthesis of aminophosphine phosphinite bidentate ligands.

Scheme 36.11 Parallel synthesis of a library of aminophosphine ligands.

The beneficial effect of surfactants on enantioselective hydrogenations in water was exploited in the synthesis of a-aminophosphinic and a-aminophosphonic acids. These compounds are stmctural analogues of a-aminocarboxylic acids and their peptides find use as herbicides, bactericides and antibiotics [150,151]. With [Rh(BPPM)(COD)]Bp4 and similar catalysts fast ractions and e.e.-s up to 98% could be obtained in water in the presence of SDS (Scheme 3.12). 

Certain chiral phosphinite or aminophosphine ligands are also useful for amino acid synthesis. Hydrogenation with a CYCPHOS-Rh complex occurs rapidly to produce high optical yields. The efficacy of this reaction is ascribed to the flexibility of the ligand, which speeds the reaction and gives a fixed chelate ring conformation (26). 

Synthesis of chiral aminophosphines from natural aminoacids. 

Of particular interest in the latter case is the use of N-NMR spectroscopy for the determination of J( P, N) data, of which there are few examples for systems having two coordinate sp -hybridised nitrogen linked to phosphorus. " Various acyclic bis(aminophosphines) have also been reported, including the imino-functional system (96), the bis(phosphino)-hydrazines (97) and -ureas (98), and the l,8-bis[bis(dialkylamino)phosphino]naphthalenes (99). There has also been significant activity in the synthesis of cyclic aminophosphines. An improved route to the four-membered ring system (100) is afforded by the reaction of phosphorus trichloride with t-butylamine in a 1 3 mole ratio in THF. Treatment of this with ammonia in THF/triethylamine at — 78°C gives (101),... 

The cyclic phosphinate (96) has been isolated from the reaction of dichloro(methyl)phosphine with the ethoxycarbonylimine derived from hexafluoroacetone. Treatment of trichloro(organo)phosphonium-hexafluorophosphate salts with dichloro(diethylamino)phosphine results in the halophosphonium salts (97). Some reactions of dichloro(-)menthylphosphine have been reported.As usual, nucleophilic displacement reactions of halogenophosphines have received attention as routes to new systems of interest as ligands.Of particular interest in this connection is a report of the synthesis of the phosphorus-functionalised calixarenes (98). Only one chlorine atom of dichloro(phenyl)-phosphine is replaced on treatment with an excess of dicyclohexylamine, enabling the stepwise synthesis of the chiral aminophosphines (99), described as air-stable solids. 

Scheme 7 displays a possibility of the synthesis of chiral 2-arylpropionic acids via the oxidative tranformation of (7 )-3-aryl-l-butenes. The requisite chiral olefins may be obtained by transition metal-catalyzed asymmetric coupling between a benzylic Grignard reagent and vinyl bromide (93 % optical yield) [28] or, more attractively, asymmetric hydrovinylation of an aromatic olefin with ethylene. The asymmetric combination of styrene and ethylene, giving the adduct 25 in 95 % ee, has been performed on a 10-kg scale with a dinuclear Ni catalyst formed from ( -allyl)NiCl2 and a unique chiral dimeric aminophosphine obtainable from (/ )-myrtenal and (5)-l-phenylethylamine [7a],... 

Aminophosphines. - The bis(V-pyrrolidinyl)phosphines (139), prepared conventionally by treatment of the appropriate organodichlorophosphine with an excess of pyrrolidine, have proved to be unusually electron-rich <7-donor ligands when compared to either tris(V-pyrrolidinyl)phosphine, or trialkyl-and triaryl-phosphines. Full details of a route to the polycylic aminophos-phirane systems (140) have now appeared. The bis(aminophosphine) (141) has been prepared and used in the synthesis of macrocyclic metal complexes. Two new chiral aminophosphine systems (142) and (143) have been prepared by transamidation of related aryl bis(dimethylamino)phosphines with a chiral amine. The chiral aminophosphine (144) has been obtained from the reaction of chlorodiphenylphosphine with the methyl ester of alanine. A range of ether-functionalised aminophosphines (145) has also been prepared. 

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