Cobalt-catalyzed biphasic hydroformylation of internal short chain olefins

Highly Selective Catalyst Systems for the Hydroformylation of Internal Olefins to Linear Aldehydes

“…With ODonnells nucleophilic glycine equivalent 12 [9] the methylenecyclopropane derivative 13, a substituted isomer of hypoglycin A in a protected form, [10] was obtained in 76 % yield (Scheme 3). Glycine methyl ester 14 a, in the presence of triethylamine in…”

“…While studying the homogeneous and biphasic [9] hydroformylation of 1-and 2-pentene in the presence of phosphanemodified cobalt catalysts, [10] we became interested in similar reactions with more active rhodium catalysts. Among the various phosphanes tested for this reaction 2,2'-bis(diphenylphosphanylmethyl)-1,1'-binaphthyl (NAPHOS, [11] a structural variation of the 2,2'-bis(diphenylphosphanylmethyl)biphenyl (BISBI) ligand), which resembles the backbone of the sterically demanding phosphites, gave the best results (Table 1).…”

“…[6] Regarding phosphane catalyst systems there has been only one recent development, which was described by van Leeuwen and co-workers, where modified xanthene ligands were used for the hydroformylation of 2-and 4-octene. [7] With these ligands linear:branched (n:i) ratios up to 90:10 and catalyst turnover frequencies (TOF) [8] of 112 h À1 were achieved for the hydroformylation of 2-octene.Herein we report the development of new rhodium catalyst systems that enable the hydroformylation of different terminal and internal olefins in excellent selectivities, which represents a substantial improvement in efficiency of this industrially important reaction.While studying the homogeneous and biphasic [9] hydroformylation of 1-and 2-pentene in the presence of phosphanemodified cobalt catalysts, [10] we became interested in similar reactions with more active rhodium catalysts. Among the various phosphanes tested for this reaction 2,2'-bis(diphenylphosphanylmethyl)-1,1'-binaphthyl (NAPHOS, [11] a structural variation of the 2,2'-bis(diphenylphosphanylmethyl)biphenyl (BISBI) ligand), which resembles the backbone of the sterically demanding phosphites, gave the best results (Table 1).…”

Synthesis of Pyrrolyl-, Indolyl-, and Carbazolylphosphanes and Their Catalytic Application as Ligands in the Hydroformylation of 2-Pentene

“…[4] While water-soluble cobalt catalysts work under milder conditions, the n/iso ratios of cobalt-catalyzed hydroformylation reactions are comparatively low. [5] In general, phosphanerhodium catalysts display much higher activities for terminal olefins than for internal olefins, which are converted very slowly with little isomerization. [6] Coordinatively unsaturated rhodium species, however, exhibit activity towards isomerization of the substrate.…”

Hydroformylation of 1-Octene Mediated by the Cobalt Complex [CoH(dchpf)(CO)2]

“…Cobaltmediated hydroformylation is well-known and has been continuously reviewed [25][26][27]. While Beller, ColeHamilton and others have reported various kinds of modifications [28][29][30][31] of the original catalytic system, there have also been computational approaches from the groups of Beller and Pringle to the Co complex-catalyzed hydroformylation [32,33]. However, not many studies describe the use of well-defined complexes with bidentate chelating P-donors [34], and none (to the best of our knowledge) report the use of isolated carbonyl-hydrido-cobalt compounds.…”