Monodentate phosphite

Recent patent activity suggests that DuPont is developing a new generation of chelating diphosphite—nickel catalysts for this technology which are significantly more active than the monodentate phosphite based catalyst system used for the last two decades (61—64). 

Switching the roles of the zinc porphyrin template and N-donor adapter provides an alternative mode for the supramolecular construction of biden-tate ligands (Scheme 32). Complex 26 derived from mixing three equivalents of template 24 with two equivalents of monodentate phosphite ligands 23 furnished a rhodium catalyst which displayed good regioselectivity toward... 

The chiral monodentate phosphites presented in Scheme 28.6 are easily prepared from a diol, phosphoms trichloride, and an alcohol. Usually, the diol is converted into the corresponding phosphoro chloridite, followed by reaction... 

Scheme 28.6 Monodentate phosphite ligands derived from BINOL or related diols.

Rhodium-catalyzed hydrogenation of enamides has been successfully performed using monodentate phosphites 17, with enantioselectivities of up to 95% being obtained [53]. The rate of hydrogenation is low in order to reach full conversion with a SCR of 500, hydrogenation is performed at a pressure of 60 bar for 20 h. The use of ligand 17 am in the rhodium-catalyzed hydrogenation of aromatic enamides resulted in ee-values of up to 95%. 

As described for monodentate phosphonite ligands, monodentate phosphite ligands have also been used in a monodentate ligand combination approach. 

Scheme 28.8 Monodentate phosphite ligands based on carbohydrates.

Reetz and Goossen et al. reported recently the asymmetric hydrogenation of a series of enol esters using monodentate phosphite ligands 17 and 24 based on a combination of BINOL and carbohydrates or simple alcohols the results of these studies are shown in Table 28.6. 

However, it is possible that the heterocatalyst becomes the dominant one, either if it is more stable and thus formed in large excess, or if it is a more active, kinetically dominant catalyst. Recently, both Reetz et al. and Feringa/Min-naard/de Vries et al. have shown that this approach can be beneficial. Earlier attempts by Chen and Xiao using mixtures of monodentate phosphites based on bisphenol and a chiral alcohol were not successful [39]. In our experience, the majority of catalysts based on mixtures of monodentate ligands show a poorer performance than the individual homo-catalysts. However, in a few instances there is a positive effect. 

In the studies conducted by Reetz, rhodium catalysts based on mixtures of monodentate phosphites, monodentate phosphonites and combinations of the two were screened in the enantioselective hydrogenation of a- and /9-N-acetyl-de-hydroamino acid esters, enamides and dimethyl itaconate [40], and a number of the more striking positive results are listed in Table 36.3. An enhanced ee-value was found mostly with combinations of two phosphonites, or one phosphonite and one phosphite, in particular when one of the ligands carries a bulky substituent and the other a small one. 

Chiral monodentate phosphites and phosphoramidites are also effective ligands for Rh-catalyzed asymmetric hydrogenation of enamide substrates. As seen in the structure of MonoPhos illustrated in Figure 1.2, combination of the mod-ihed BINOF backbone and the amine part gives a structural variety to this type of ligand. Combinatorial methods are effective for optimization of the chiral structures.Elucidation of the hydrogenation mechanism catalyzed by the MonoPhos-Rh complex is in progress." ... 

The same nanofiltration experiments were performed with a 50-A ultrafiltration membrane (available from US Filter/Membralox, Warrendale, PA,USA), this time with a monodentate phosphite ligand (24) used for comparison and toluene as the solvent (Table V). Both higher retentions and flux rates for the dendrimers were obtained relative to what was observed with the reverse osmosis membranes. Dendrophite G4 was used in three subsequent reactions carried out with this procedure. 

For examples of asymmetric catalyses with BlNOL-derived monodentate phosphites, phosphonites, and phosphoramidites, see a) M. T. Reetz, G. Mehler, Angew. Chem. 2000, 112, 4047 Angew. Chem. Int. Ed. 2000, 39, 3889 ... 

The hydrocyanation of alkenes [1] has great potential in catalytic carbon-carbon bond-formation because the nitriles obtained can be converted into a variety of products [2]. Although the cyanation of aryl halides [3] and carbon-hetero double bonds (aldehydes, ketones, and imines) [4] is well studied, the hydrocyanation of alkenes has mainly focused on the DuPont adiponitrile process [5]. Adiponitrile is produced from butadiene in a three-step process via hydrocyanation, isomerization, and a second hydrocyanation step, as displayed in Figure 1. This process was developed in the 1970s with a monodentate phosphite-based zerovalent nickel catalyst [6],... 

Tolman, Druliner, and McKinney [5] were pioneers in nickel-catalyzed hydrocyanation they used monodentate phosphites mainly to understand and improve the adiponitrile process. Although bidentate ligands give better results in the adiponi-trile process [21], mechanistic studies with these systems are rare bidentate phos-phinites have been studied in the asymmetric hydrocyanation of MVN [19]. 

Mono- and dihydroaminomethylation of olefins was performed with dicarbonyl-2,4-pentanedionerhodium containing a monodentate phosphite ligand as the catalyst under moderate pressures. The reaction has high region-specificity with yields exceeding 90%. 

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