Catalysts borohydride reduction

Reduction to alcohols (Section 15 2) Aide hydes are reduced to primary alcohols and ketones are reduced to secondary alcohols by a variety of reducing agents Catalytic hydrogenation over a metal catalyst and reduction with sodium borohydride or lithium aluminum hydride are general methods... 

Optically active /3-ketoiminato cobalt(III) compounds based on chiral substituted ethylenedi-amine find use as efficient catalysts for the enatioselective hetero Diels Alder reaction of both aryl and alkyl aldehydes with l-methoxy-(3-(t-butyldimethylsilyl)oxy)-1,3-butadiene.1381 Cobalt(II) compounds of the same class of ligands promote enantioselective borohydride reduction of ketones, imines, and a,/3-unsaturated carboxylates.1382... 

More initial rate data for monoene substrates have appeared using as catalysts RhCl(CO)P2, HRh(CO)P3 (110, 158), and Rh(NO)P3 (110, 157), where P is a tertiary phosphorus donor. Borohydride reduction of Rh(NO)(PPh3)2Cl gives an active catalyst (159). 

Borohydride reduction of NiCl2 in dimethylformamide or dimethyl-acetamide leads to very active catalysts, thought to be homogeneous, for hydrogenation of monoolefins, unsaturated fats, cyclic dienes to monoenes, and saturated aldehydes and ketones (165, 538, 539). Cobaltous chloride systems have also been used (540). 

Brimble and coworkers176 studied the asymmetric Diels-Alder reactions of cyclopentadiene with chiral naphthoquinones 272 bearing different chiral auxiliaries. The highest endo and facial selectivities were obtained using zinc dichloride as the Lewis acid catalyst and (—)-pantolactone as the chiral auxiliary. Thus, the reaction between cyclopentadiene and 272 afforded a 98 2 mixture of 273 and 274 (equation 76). The chiral auxiliary was removed easily by lithium borohydride reduction. 

Lactitol is a disaccharide sugar alcohol prepared by reduction of the glucose residue to a sorbitol group. It is prepared by hydrogenation of a lactose solution hydrogenation at 100°C for 6 hr and 8825 kPa with a Raney nickel catalyst produces lactitol in nearly quantitative yield (van Velthuijsen 1979 Linko et al. 1980). Hydrogenation of lactose with sodium or calcium amalgam catalysts and reduction with sodium borohydride (Scholnick et al 1975) have also been successful. 

In other reports, /i-cyclodcxtrins have been used to induce asymmetry in borohydride reduction of ketones,166 a diastereoselective reduction has been controlled167 by a real lyltricarbonyl iron lactone tether , a phosphinamide has been combined with a dioxaborolidine unit as an activated, directed catalyst for ketone reduction,168 reductive amination using benzylamine-cyanoborohydride converts 3-hydroxy ketones into syn-1,3-amino alcohols,169 l-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)propan-l-one has been reduced diastereoselectively,170 and production of chiral alcohols via (i) Itsuno-Corey and Brown procedures171 and (ii) lithium aluminium hydride modified by chiral nucleophiles172 has been reviewed. 

Consequently, Dehmlow and coworkers modified the cinchona alkaloid structure to elucidate the role of each ofthe structural motifs of cinchona alkaloid-derived chiral phase-transfer catalysts in asymmetric reactions. Thus, the quinoline nucleus of cinchona alkaloid was replaced with various simple or sterically bulky substituents, and the resulting catalysts were screened in asymmetric reactions (Scheme 7.2). The initial results using catalysts 8-11 in the asymmetric borohydride reduction of pivalophenone, the hydroxylation of 2-ethyl-l-tetralone and the alkylation of SchifF s base each exhibited lower enantiomeric excesses than the corresponding cinchona alkaloid-derived chiral phase-transfer catalysts [14]. 

High enantioselectivities (up to 94%) are obtained in the sodium borohydride reduction of aliphatic ketones using a tartaric acid-derived boronic ester (TarB-N02) as a chiral catalyst. A mechanism (Scheme 14) involving an acyloxyborohydride intermediate has been postulated.319... 

The use of numerous polymer-supported optically active phase transfer catalysts was further extended by Kelly and Sherrington11351 in a range of phase transfer reactions including a variety of displacement reactions, such as sodium borohydride reductions of prochiral ketones, epoxidation of chalcone, addition of nitromethane to chalcone and the addition of thiophenol to cyclohexanone. Except in the chalcone epoxidation, all the examined resin catalysts proved to be very effective. However, with none of the chiral catalyst system examined was any significant ee achieved. The absence of chiral induction is a matter of debate, in particular over the possible reversibility of a step and the minimal interaction within an ion pair capable of acting as chiral entities in the transition state and/or the possible degradation of catalysts and leaching. 

TABLE 9.4 Hydrogenation of Nitrobenzene over Platinum Metal Catalysts Produced In Situ by Borohydride Reduction 2 ... 

Three methods for catalyst activation are currently in use these include (i) hydrogen or deuterium reduction, (ii) borohydride reduction,86-87 and (Hi) self-activation.88,89 Self-activation [Eq. (19)]... 

Reduction of aqueous or ethanolic solutions of inorganic salts with sodium or potassium borohydride is now the most useful procedure for catalyst activation. Reduction is fast and efficient at room temperature, and, particularly in the case of nickel, a catalyst more active than Raney nickel can be obtained.66 Instead of borohydride, silicon hydrides such as tribenzylsilane have been used for the reduction to produce active platinum catalysts.75... 

Precursor of Useful Chiral Ligands. OPEN is widely used for the preparation of chiral ligands. Organometallic compounds with these ligands act as useful reagents or catalysts in asymmetric induction reactions such as dihydroxylation of olefins, transfer hydrogenation of ketones and imines, Diels-Alder and aldol reactions, desymmetrization of meso-diols to produce chiral oxazolidinones, epoxidation of simple olefins, benzylic hydroxylation, and borohydride reduction of ketones, imines, and a,p-unsaturated carboxylates. ... 

The Co(bipy)3+ ion is a useful catalyst for a number of borohydride reductions, e.g., organic nitro compounds are reduced smoothly to amines at pH 6.5-7 the true reducing agent is Co(bipy)3+. The oxidation-reduction potential for Co(I)/Co(II) is 0.91 volt (vs. standard calomel electrode in 50% aqueous ethanol) and this should fall between the potentials of the other reactants (709). Catalytic reductions of organic halogen compounds may be achieved (436), and the system is reactive to small molecules such as NgO (38). 

When borohydride reductions are carried out in the presence of either a chiral phase transfer catalyst or a chiral crown ether, asymmetric reduction of ketones occurs but optical yields are low. In the reduction of acetophenone with NaBH4 aided with a phase transfer catalyst (57), 10% ee was obtained. Similarly, reduction of acetophenone with NaBH4 in the presence of the chiral crown ether (58) was ineffective (6% ee)J Sodium borohydride reduction of aryl alkyl ketones in the presence of a protein, bovine semm albumin, in 0.01 M borax buffer at pH 9.2 affords (R)-carbinols in maximum 78% cc. ... 

Titanium(II) reagents have also been used to reduce aliphatic nitro compounds to amines halo, cyano and ester groups are not reduced. Sodium borohydride, in the presence of catalytic amounts of nickel(II) chloride, reduces a variety of aliphatic nitro compounds to amines. Nickel boride (Ni2B) is an active catalyst for reductions of primary, secondary and tertiary nitro aliphatic compounds to amines. The reduction of nitrocyclohexane (45) yields cyclohexylamine (47) as well as small amounts of dicyclohexylamine (49), the latter being formed via reaction of intermediates (46) and (48 equation 28). 

Catalytically active species have been prepared by the alkali borohydride reduction of a number of different metal salts. Some of these catalysts are metal borides while others appear to be the reduced metal. 

The borohydride reductions are commonly run in an inert atmosphere as contact with air during catalyst preparation leads to a significantly less active material. Brief exposure to air after formation of the catalyst, however, does not seem to significantly affect the activity of a P-2 catalyst.26 More reproducible data were obtained when the reaction solvent was deaerated before the addition of the reducing agent. 

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