Rhodium complexes oxidation-reduction conversion

Using two types of specially synthesized rhodium-complexes (12a/12b), pyruvate is chemically hydrogenated to produce racemic lactate. Within the mixture, both a d- and L-specific lactate dehydrogenase (d-/l-LDH) are co-immobilized, which oxidize the lactate back to pyruvate while reducing NAD+ to NADH (Scheme 43.4). The reduced cofactor is then used by the producing enzyme (ADH from horse liver, HL-ADH), to reduce a ketone to an alcohol. Two examples have been examined. The first example is the reduction of cyclohexanone to cyclohexanol, which proceeded to 100% conversion after 8 days, resulting in total TONs (TTNs) of 1500 for the Rh-complexes 12 and 50 for NAD. The second example concerns the reduction of ( )-2-norbornanone to 72% endo-norbor-nanol (38% ee) and 28% exo-norbornanol (>99% ee), which was also completed in 8 days, and resulted in the same TTNs as for the first case. 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

This hydrocarboration method is a valuable tool in industrial and laboratory synthesis, since it allows introduction of the one-carbon unit of carbon monoxide into unsaturated substrates and construction of new carbon skeletons with aldehyde functions or derivatives thereof formed by reduction, oxidation, condensation and other conversions. Hydroformylation, mainly catalyzed by cobalt, rhodium, or platinum complexes is an unsymmetrical 1,2-addition leading to linear and branched products if terminal olefins are used as the substrate. Since linear products are normally the industrial products wanted54, considerable efforts have concentrated on the control of regiochemistry. Other problems of the hydroformylation method arise from side reactions such as hydrogenation, double bond migration, and subsequent reactions of the products (e.g., condensation, reduction, dccarbonylation)54. 

Ben2X>quinones exhibit redbx behavior at easily acoessiUe potentials and coordinate to metal ions. Catechols, products of die two-electron reduction of o-benzocpiinones, are also good ligands, giving rise to catecholate complexes. o-Benzoquinones have been used to obtain catecholate complexes via oxidative addition.203 For example, the reaction of fra s-[RhQ(CO)(PPh3)2] with tetrachloro-l,2-benzoquinone results in the conversion of the four-coordinate rhodium(1) complex to a six-coordinate rhodium(m) catecholate complex. Scheme 8.28 ... 

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