Primary phosphine ligands

The primary phosphine ligand PHg appears to be very effective in causing the aggregation of mononuclear units into clusters, if the preliminary reports of the compounds it forms prove to be accurate (255). 

Beller and coworkers found in 2009 that alkynes react with amines under the CO pressure (20 bar) in the presence of catalytic amounts of [Fe3(CO)i2] to the corresponding succinimide in moderate to excellent yields (Scheme 35) [110]. Various terminal and internal alkynes and ammonia or primary amines are adaptable for this transformation. Furthermore, [Fe(CO)s] as an iron source showed high activity. The catalytic activity, however, decreased considerably when a phosphine ligand such as PPh3 and ( Bu)2P("Bu) was employed. 

One exception to the use of primary phosphines is in the reported syntheses of the catASium M dass of ligands 20 [46-49]. In one report, reaction of the cyclic sulfate with P(TMS)3 yields the TMS-protected secondary phospholane, which could then be reacted with the appropriate 1,2-dichloro spedes [46]. An alternative procedure to the same intermediate involves preparation of 1-phenyl-phospholane via the bismesylate, subsequent lithium-induced P-Ph deavage, and quenching with TMSC1 [49]. The ligand based on 2,3-dichloromaleic anhydride (20a originally referred to as MalPHOS [46]) has been shown to be effective for the chiral reduction of a- and /1-deliydroarnino acid derivatives and itaconate derivatives. 

By Addition ofP—H to Unsaturated Compounds. This route continues to be exploited for the synthesis of polydentate tertiary phosphine ligands. Thus base-catalysed addition of diphenylvinylphosphine to the secondary phosphine (25) affords (26).23 Neopentylpolytertiaryphosphines, e.g. (27), have been similarly prepared24 by addition of primary or secondary phosphines to vinylphosphines (or the related phosphine sulphides, followed by a desulphurization step). 

Aqueous organometalHc catalysis allows the use of NH3-solutions in water for the direct synthesis of amines from olefins in a combined hydroformylation/reductive amination procedure (Scheme 4.19). The hydroformylation step was catalyzed by the proven Rh/TPPTS or Rh/BINAS (44) catalysts, while the iridium complexes formed from the same phosphine ligands and [ IrCl(COD) 2] were found suitable for the hydrogenation of the intermediate imines. With sufficiently high NH3/olefin ratios (8/1) high selectivity towards the formation of primary amines (up to 90 %) could be achieved, while in an excess of olefin the corresponding... 

The application of the desymmetrization method can be extended to a bicyclic system containing two primary acetate leaving groups (Scheme 8E.16). By using the chiral pyridine-phosphine ligand 49, the diacetate could be converted into the allylic amine in 93% yield and 89% ee [70],... 

Fig. 10. Multiple derivatization of purines including palladium-catalyzed reaction at the poorly reactive C2 position, (a) NaBH(OAc)3, 1% HOAc, THF (b) 59 (0.5 equiv.), 2,6-dichloropurine (1 equiv.), DIEA (1.5 equiv.), BuOH 80° (c) R2OH, PPh3, DiAD (1.5 2 1.3) in excess, THF, RT (d) boronic acids (5 equiv.), 7% Pd2(dba)3, 14% carbene ligand, Cs2C03 (6 equiv.), 1,4-dioxane, 90°, 12 h (e) anilines (5 equiv.), 7% Pd2(dba)3, 14% carbene ligand, KO Bu (6 equiv.), 1,4-dioxane, 90°, 12 h (f) phenols (5 equiv.), 7% Pd2(dba)3, 28% phosphine ligand, K3P04 (7 equiv.), toluene, 90°, 12 h (g) primary or secondary amines (5 equiv.), 90°, 12 h.

Results on the amination of pyridyl halides conducted with two phosphine ligands and two different palladium precursors have been published (Table 2) [123]. The most general palladium precursor proved to be palladium acetate. Again, BINAP was found to be generally effective for amination with either primary or secondary amines. However, yields were lower with unbranched primary amines than those with branched amines, such as cydo-... 

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