Bidentate phosphite ligand

Under high pressure, the reaction favors the formation of kinetic adducts (10) and (11) with precursor (6). Further regioselectivity and yield enhancement could be achieved with the bidentate phosphite ligand tpdp (12) as illustrated in Scheme 2.3 [11]. 

Reaction of the cyclopropyl-substituted pivalate (25) with dimethyl benzylidenema-lonate in the presence of a palladium catalyst gave a mixture of alkylidenecyclo-propane (26) and vinylcyclopropane (27). The ratio of these two adducts is found to be quite sensitive to the choice of ligand and solvent. While triisopropyl phosphite favors the formation of the methylenecyclopropane (26), this selectivity is completely reversed with the use of the bidentate phosphite ligand dptp (12). Interestingly there was no evidence for any products that would have derived from the ring opening of the cyclopropyl-TMM intermediate (Scheme 2.8) [18]. 

Slagt. V.F., van Leeuwen, P.W.N.M. and Reek, f.N.H. (2003) Midticomponent porphyrin assemblies as functional bidentate phosphite ligands for regioselective rhodium-catalyzed hydroformylation. Angew. Chem., Int. Ed., 42, 5619-5623. 

Much progress has been made on regioselective hydroformylation of terminal alkenes in favor of the linear product. In particular bidentate phosphine or phosphite ligands, which have a natural bite angle 9 of about 110°, will favor the linear product. The most successful ligand types are BISBI [49, 50], BIPHEPHOS [51,52], and XANTPHOS systems (Scheme 8) [53]. 

Bidentate phosphorus ligands based on BINOL, such as phosphonite 23, phosphites 24 and 25, and phosphoramidite 26 (Tab. 7.2), with various bridging units were introduced by the groups of Reetz, Chan, and Waldmann [48-50]. Excellent enantioselectivities - up to 96% for ligand 23, for instance - were found. 

Takemoto and his co-workers developed asymmetric allylic alkylation of allylic phosphates with (diphenyl-iminolglycinates as carbon-centered nucleophiles (Equation (56))/" " In this reaction system, use of optically active bidentate phosphites 142 bearing an (ethylthio)ethyl group as chiral ligands promotes the allylic alkylation, and chiral /3-substituted a-amino acids are obtained with an excellent enantioslectivity. 

A rhodium-catalyzed hydroformylation was also carried out with the bicyclic terpenes [S-pinene and camphene [44, 45]. The influence of phosphine and phosphite ligands (L) on the formation of the different product isomers of the hydroformylation of [S-pinene was studied by adding different mono- and bidentate ligands. However, the basicity of the ligands proved to be relevant for favoring the c/.v-isomer. A steric influence of the ligands to favor one isomer was not found (Scheme 14). 

Whereas bidentate phosphites and phosphonites are excellent ligands for rhodium-catalyzed asymmetric hydrogenation, bidentate phosphoramidites (not shown) gave very poor results with low reaction rates and enantioselectivities. Results of a number of other monodentate phosphoramidites in the asymmetric hydrogenation of. V-acetyl dehydrophenylalanine derivatives are shown in Table 14.7.31-35-36-39-40... 

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