Directed Hydroformylation

Due to the heterogeneity of the recently advanced solid-support catalyst for the hydroformylation, direct structural information on catalyst surface has been collected by extended X-ray absorption fine structure (EXAFS). Iwasawa is the first to directly characterize the structure of dimeric rhodium complexes supported on... 

In the hydroformylation of an olefin not only are aldehydes formed that directly correspond with the used olefin isomer but also all the other theoretically possible isomeric 2-alkyl-branched aldehydes [49] ... 

The catalytic hydroformylation of alkenes has been extensively studied. The selective formation of linear versus branched aldehydes is of capital relevance, and this selectivity is influenced by many factors such as the configuration of the ligands in the metallic catalysts, i.e., its bite angle, flexibility, and electronic properties [152,153]. A series of phosphinous amide ligands have been developed for influencing the direction of approach of the substrate to the active catalyst and, therefore, on the selectivity of the reaction. The use of Rh(I) catalysts bearing the ligands in Scheme 34, that is the phosphinous amides 37 (R ... 

Ziegler-Natta catalyst for polymerization of alkenes. Considerable attention has been directed to double-bonded Fischer carbenes of Cr and W, the Schrock carbenes of Ta and Ti, and cyclic polyene ligands of Fe, Co, Cr, and U. Carbonyls of transition metals from groups 6 to 10 of the periodic table include both the monomeric compounds such as Cr(CO)g, Fe(CO)5, Ni(CO)4 and those with two metal groups such as Mn2(CO)io and Co2(CO)s, which is used industrially for hydroformylation. Although their source has not been identified, it has been shown that volatile compounds from landfills contain carbonyls of Mo and W (Feldmann and Cullen 1997). 

Hydroxymethyl ati on of Polybutadiene - The hydroformyl ated PBD reaction solution obtained above was subsequently hydrogenated directly using the following reaction conditions Hydroformyl ated PBD solution = 75 ml, RuC1H(C0)(P(CcHc)3)3 = 1.05 mol/m3, Hydrogen pressure = 600 psig, Temperature = 1 0 C. 

Abstract Recent advances in synthetic aspects of the rhodium-catalyzed hydroformylation of alkenes are reviewed. Emphasis is given to practical improvements, efficient new catalysts for regioselective and enantioselective hydroformylation, and to applications of the reaction in organic synthesis. Furthermore, new developments in directed hydroformylation are covered as well as new approaches toward efficient hydroformylation catalysts employing the concept of self-assembly. 

The regioselectivity of the hydroformylation of alkenes is a function of many factors. These include inherent substrate preferences, directing effects exerted by functional groups as part of the substrate, as well as catalyst effects. In order to appreciate substrate inherent regioselectivity trends, alkenes have to be classified according to the number and nature of their substitution pattern (Scheme 3) [4]. 

Hydroformylation of a range of 1,1-di- and 1,1,2-trisubstituted unsatur-ated esters yields quaternary aldehydes (Table 1, entries 1-8). Hence, the regiochemistry-directing influence of the electron-withdrawing ester function overcompensates Keuleman s rifle. Furthermore, hydroformylation of 1,2-disubstituted unsaturated esters occurred with high a-selectivity and chemoselectivity (Table 1, entries 9 and 10). As a side reaction hydrogenation of the alkene has been observed [41]. 

Alternatively, substrate control of diastereoselectivity can rely on attractive catalyst substrate interactions. This requires in general special functional groups which allow for a directed hydroformylation, which is summarized in Sect. 6 (vide infra). 

A new chiral variant of the o-DPPB catalyst-directing group, the or-f/zo-diphenylphosphanylferrocene-carboxylalc (o-DPPF) has been developed. Employing this chiral directing group, a desymmetrizing hydroformylation of... 

Breit B (2007) Directed Rhodium Catalyzed Hydroformylation of Alkenes. Top Organomet Chem, published online... 

Finally, research efforts to replace hexafluorophosphate (and other halogen-containing) ionic liquids by some cheap and halogen-free ionic liquids in the Rh-catalysed hydroformylation should be mentioned. The first attempts in this direction were made by Andersen et al. [10] These authors investigated the hydroformylation of... 

The hydrogen partial pressure has a small but reproducible effect on the hydroformylation product composition. The direction of the change found was the same as for carbon monoxide partial pressures the higher PH% experiments gave higher percentages of n-aldehyde. 

With cobalt catalysts, hydroformylation of ethyl cinnamate gave 91% of the hydrogenation product ethyl hydrocinnamate (15) and only 8% of the expected lactone, 16 (72). However, rhodium catalysis was effective in directing the reaction in favor of hydroformylation (70). The comparative results obtained with cobalt and rhodium are outlined in Table XXV. 

Today, iridium compounds find so many varied applications in contemporary homogeneous catalysis it is difficult to recall that, until the late 1970s, rhodium was one of only two metals considered likely to serve as useful catalysts, at that time typically for hydrogenation or hydroformylation. Indeed, catalyst/solvent combinations such as [IrCl(PPh3)3]/MeOH, which were modeled directly on what was previously successful for rhodium, failed for iridium. Although iridium was still considered potentially to be useful, this was only for the demonstration of stoichiometric reactions related to proposed catalytic cycles. Iridium tends to form stronger metal-ligand bonds (e.g., Cp(CO)Rh-CO, 46 kcal mol-1 Cp(CO)Ir-CO, 57 kcal mol ), and consequently compounds which act as reactive intermediates for rhodium can sometimes be isolated in the case of iridium. 

A method for observing intermediates directly in the reaction cycle is in situ IR spectroscopy under reaction conditions. As early as 1975, Penninger published a contribution concerning in situ IR spectroscopic studies of cobalt carbonyl modified by tri-u-butylphosphine as a hydroformylation catalyst [58] at relatively low catalyst concentrations of 2 mmoll-1. The observed carbonyl... 

Further information on the reaction intermediates is achieved by in situ NMR experiments. Because the signals in NMR spectra depend upon the concentration of the investigated species, a quantitative treatment is possible. Bianchini and coworkers investigated the hydroformylation of 1-hexene [62], using high-pressure NMR spectroscopy to evaluate the influence of synthesis gas on the equilibria of rhodium triphenylphosphine species. They were able to establish at least four resting states of rhodium (catalyst species that do not participate directly in the reaction). When synthesis gas interacted with... 

If the hydroformylation of olefins is conducted in the presence of aromatic hydrazines and Bronsted or Lewis acids indoles can be obtained directly in one pot [91-93,95]. Hydroformylation of the olefin gives an intermediate aldehyde, which is trapped immediately by the present aromatic hydrazine as an aromatic hydrazones similar to the formation of imines under hydroformylation conditions. Under acid mediation these aromatic hydrazones undergo a Fischer indolization, consisting of a [3,3]-sigmatropic rearrangement followed by a cyclization and elimination of ammonia (Scheme 38). 

---