Phenylphosphinates synthesis

Tan, Y.N., Yang, J., Lee, J.Y. and Wang, D.l.C. (2007) Mechanistic study on the bis(p-sulfonatophenyl)phenylphosphine synthesis of monometallic Pt hollow nanoboxes using Ag -Pt core-shell nanocubes as sacrificial templates. Journal of Physical Chemistry C, 111, 14084. 

This group has also developed two ring-contraction systems of potential use in crown synthesis. In the first of these, extrusion of a phenylphosphine oxide unit results from treatment with alkoxide ion. In the second, similar conditions initiated decarbonyla-tion of a bis-pyridyl ketone Despite the apparent potential of these methods for crown synthesis, direct formation of crowns by processes which involve them do not appear to have enjoyed great success thus far. 

Although of limited success, this Ni-catalysed coupling strategy builds on a previous report of the successful, direct synthesis of poly(4,4 -diphenylphenyl-phosphine oxide) (70c) from bis(p-chlorophenyl)-phenylphosphine oxide (71) (Scheme 21) [66]. The white soluble material (70c) (Aj ax 280 nm) was found to have a single phosphorus environment by NMR spectroscopy, a comparatively high molecular weight (Mn= 15,300) together with a low molecular... 

The possibility of carrying out a multistep synthesis makes it possible to obtain P,B-containing derivatives from unstable intermediate a-hydroxyalkylphosphines. Thus, phenylphosphine, salicylic aldehyde, phenylboric acid anhydride, and triethylamine interact to give a bicyc-lic product—2,8,9-trioxa-1 -borata-4-phospha-6,7 -benzobicyclo [3,3,3] nonane (115) [Eq. (74)] (87IZV2118 89IZV946). In this case an aldehyde takes part in the reaction opening up new synthetic possibilities. 

Oleksyszyn, J., 1-N-Alkylaminoalkanephosphonic and 1-N-alkylaminoalkyl-phenylphosphinic acids, Synthesis, 722, 1980. 

Table 11 Synthesis of optically active alkenylphosphinates via palladium-catalyzed H-P addition of (-)-menthyl phenylphosphinate...

Several methods are available for the synthesis of ring systems comprised of the heavier group 13 and group 15 elements. Six-membered AI3E3 rings (E = P, As) are obtained from the reactions of (Mes AlH2)2 with phenylphosphine or... 

Cyclopentanone synthesis. The palladium reagent (I), as well as tetrakis(tri-phenylphosphine)palladium, promotes a 1,3-alkyl shift from oxygen to carbon with no allylic inversion. Two typical examples are formulated.1... 

A further extension of this type of synthetic sequence is illustrated by the cyclization of 2-cyanoethyl(o-cyanophenyl)-phenylphosphine to the corresponding o-enaminenitrile followed by hydrolysis with acid to form 2,3-dihydro-l-phenyl-4(lH)-phosphinolinone.8 The only other reported synthesis of this... 

A stereospecific synthesis of aziridine 266 has been reported by Ittah et al. from arene oxide 1 by treatment with sodium azide, followed by tri-phenylphosphine reaction. The reaction proceeds via a phosphonium hydroxide intermediate (267).157... 

The advantages and disadvantages of Rh(DIPAMP) are summarized in Table 12.1. The catalyst precursor, 13, is air-stable, which simplifies handling operations on a manufacturing scale. Despite these advantages, ligand synthesis is very difficult. After the initial preparation of menthylmethyl-phenylphosphinate (16), the (/f),-isomer is separated by two fractional crystallizations (Scheme... 

Asrar, J., Berger, P. A., and Hurlbut, J., Synthesis and characterization of a fire-retardant polyester Copolymers of ethylene terephthalate and 2-carboxyethyl(phenylphosphinic) acid, J. Polym. Sci., Polym. Chem. Edit., 1999, 37, 3119-3128. 

Biphenyl bond formation has been achieved in the diiodobiaryl derivative 41 by an intramolecular aryl halide coupling reaction promoted by tetrakis(tri-phenylphosphine) nickel. This short and efficient route gave the dibenzazonine 42 in good yield (42) (Scheme 9). In a similar way, tetrasubstituted derivative 43 was successfully coupled with the more easily prepared tris(triphenylphos-phine)nickel, giving 44 in 62% yield. Subsequent debenzylation led to the most efficient synthesis of dibenzazonine 35a reported to date (43). 

Synthesis of butyl [1-(benzylamino)-2, 2-(diethoxyethane]phenylphosphinate, 47 (Scheme 22)"... 

Synthesis of (-I-) calanolide A (Scheme 8-11) was achieved by enzyme catalyzed resolution of the aldol products ( )-53. Compound 7 with acetaldehyde by aldol reaction in the presence of LDA/TiCU stereoselectively produced a mixmre of ( )-53 and ( )-54 (94% yield), the ratio of which was 96 4. ( )-53 was then resolved by lipase AK-catalyzed acylation reaction in the presence of tert-butyl methyl ether and vinyl acetate at 40 °C to obtain 41% yield of (+)-55 and 54% yield of the acetate (—)-56. Mitsunobu cyclization of (+)-55 in the presence of tri-phenylphosphine and dielthyl azodicarboxylate afforded 63% yield of (-l-)-43 with 94% ee as determined by chiral HPLC. Luche reaction on (+)-43 with CeCla 7H2O and triphenyl phosphine oxide and NaBH4 in the presence of ethanol at 30 °C gave the crude product. It was purified by column chromatography on silica gel to give 78% yield of a mixture containing 90% of (+)-calanolide A and 10% (+)-calanohde B, which were further separated by HPLC. 

Several syntheses of l,3-dithia-2,4-diphosphetane derivatives may be considered as formally proceeding via dimerization through P=S bonds,analogous to the formation of 1,3-dithietanes by dimerization of thiocarbonyl compounds (Section XXXVI.3.A). These reactions include indirect methods involving the addition of elemental sulfur to aminoiminophosphines (e-g., the synthesis of 618) or phenylphosphine and treatment of thiophenol with P4Sio, ° as well as direct... 

The first enantioselective synthesis of 1-aminoalkylphosphinic acids (319) based on the addition of phenylphosphinate (320) to chiral imines (321) and standard removal of protecting groups from the adducts (322) has been realized (Scheme 86). 

Free radical-induced additions have been used in the synthesis of a range of phosphines bearing other nucleophilic groups, e.g., (41), useful for specific peptide bond cleavage of proteins.A further example of the formation of the phosphorinanone system by addition of phenylphosphine to a divinyl ketone derivative has been described.Two reports have appeared of the addition of secondary phosphines to maleic anhydride and related activated olefins, to give functionalised tertiary phosphines, e.g., (42). A route to allylphosphines is provided by base-... 

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