Organic carbonyl compounds, reductive

Beller and coworkers reported hydrosilylation reactions of organic carbonyl compounds such as ketones and aldehydes catalyzed by Fe(OAc)2 with phosphorus ligands (Scheme 21). In case of aldehydes as starting materials, the Fe(OAc)2/PCy3 with polymethylhydrosiloxane (PMHS) as an H-Si compound produced the corresponding primary alcohols in good to excellent yields under mild conditions [67]. Use of other phosphorus ligands, for instance, PPhs, bis(diphenylphosphino) methane (dppm), and bis(diphenylphosphino)ethane (dppe) decreased the catalytic activity. It should be noted that frans-cinnamaldehyde was converted into the desired alcohol exclusively and 1,4-reduction products were not observed. 

The direct reductive amination (DRA) is a useful method for the synthesis of amino derivatives from carbonyl compounds, amines, and H2. Precious-metal (Ru [130-132], Rh [133-137], Ir [138-142], Pd [143]) catalyzed reactions are well known to date. The first Fe-catalyzed DRA reaction was reported by Bhanage and coworkers in 2008 (Scheme 42) [144]. Although the reaction conditions are not mild (high temperature, moderate H2 pressure), the hydrogenation of imines and/or enam-ines, which are generated by reaction of organic carbonyl compounds with amines, produces various substituted aryl and/or alkyl amines. A dihydrogen or dihydride iron complex was proposed as a reactive intermediate within the catalytic cycle. 

Scheme 42 Direct reductive amination of organic carbonyl compounds...

CO into a metal-hydrogen bond, apparently analogous to the common insertion of CO into a metal-alkyl bond (6). Step (c) is the reductive elimination of an acyl group and a hydride, observed in catalytic decarbonylation of aldehydes (7,8). Steps (d-f) correspond to catalytic hydrogenation of an organic carbonyl compound to an alcohol that can be achieved by several mononuclear complexes (9JO). Schemes similar to this one have been proposed for the mechanism of CO reduction by heterogeneous catalysts, the latter considered to consist of effectively separate, one-metal atom centers (11,12). As noted earlier, however, this may not be a reasonable model. 

As a result of the hydridic nature of the hydrogen attached to boron, amine-boranes are interesting and useful reducing agents and have been employed in the reduction of numerous organic carbonyl compounds. They have been utilized in studying the kinetics and mechanism of hydride reactions and are precursors for the synthesis of substituted boranes, borazines, boronium ions, higher boron hydrides, and carboranes. 

Insertion of organic carbonyl compounds into metal-hydrogen bonds is important in organic synthesis. The reductions of esters, ketones, and aldehydes by main group hydrides and complex hydrides are of particular importance, but since the primary products of insertion are not characterized, they are not considered here . ... 

Well-defined arene complexes of Group 4 metals in various oxidation states have been isolated. The air- and moisture-sensitive complexes Ti(r -arene)2 (56) have a sandwich structure similar to that of the related chromium compounds [176-178]. They have been used for deoxygenation of propylene oxide and coupling reaction of organic carbonyl compounds [179]. The first synthesis of 56 was cocondensation of metal vapor with arene matrix [176]. Two more convenient methods are reduction of TiCl4 with K[BEt3H] in arene solvent [180] and reaction of TiCl4(THF)2 with arene anions followed by treatment with iodine [170,176]. The latter method involves the formation of an anionic titanate complex, [Ti(ri -arene)2] (57), which can also be formed from KH and 56 [181]. 

With benzaldehyde, A1H reduction is accompanied by addition of the A1—C bond to the carbonyl group 296). Indeed, it is generally true to say that when organic carbonyl compounds react with tri-l-alkyl alanes or triaryl alanes, this addition of A1C to the carbonyl group is the main reaction. The following are some examples 176, SOI) ... 

Alcohols are among the most versatile of all organic compounds. They occur widely in nature, are important industrial 7, and have an unusually rich chemistry. The most widely used methods of alcohol synthesis start with carbonyl compounds. Aldehydes, ketones, esters, and carboxylic acids are reduced by reaction with LiAlH4. Aldehydes, esters, and carboxylic acids yield primary alcohols (RCH2OH) on reduction ketones yield secondary alcohols (R2CHOH). 

D. Caine, Reduction and related reaction of a, ji-unsaturated carbonyl compounds with metals in liquid ammonia. Organic Reaktions, Vol. XXIII, 1 (1976). 

Development of new reduction systems that reduce sterically hindered compounds The reported examples of reduction of carbonyl compounds are usually for the substrates that can be easily reduced such as methyl ketones. Since the demand for reduction of various types of compounds is increasing, investigation of new biocatalytic reductions is required. Photosynthetic organisms are not investigated yet, and they may have new type of enzymes, which can reduce sterically hindered compounds. 

Several methods are available for reductive removal of carbonyl groups from organic compounds. Reduction to methylene groups or conversion to alkenes can be achieved. 

Ihmels H, Otto D (2005) Intercalation of Organic Dye Molecules into Double-Stranded DNA - General Principles and Recent Developments. 258 161-204 Iida H, Krische MJ (2007) Catalytic Reductive Coupling of Alkenes and Alkynes to Carbonyl Compounds and Imines Mediated by Hydrogen. 279 77-104 Imai H (2007) Self-Organized Formation of Hierarchical Structures. 270 43-72 Indelli MT, see Chiorboli C (2005) 257 63-102 Inoue Y, see Borovkov VV (2006) 265 89-146 Ishii A, Nakayama J (2005) Carbodithioic Acid Esters. 251 181-225 Ishii A, Nakayama J (2005) Carboselenothioic and Carbodiselenoic Acid Derivatives and Related Compounds. 251 227-246... 

Nitro compounds are versatile precursors for diverse functionalities. Their conversion into carbonyl compounds by the Nef reaction and into amines by reduction are the most widely used processes in organic synthesis using nitro compounds. In addition, dehydration of primary nitro compounds leads to nitrile oxides, a class of reactive 1,3-dipolar reagents. Nitro compounds are also good precursors for various nitrogen derivatives such as nitriles, oximes, hydroxylamines, and imines. These transformations of nitro compounds are well established and are used routinely in organic synthesis. 

Cenini, S. Ragaini, F. In Reductive Carbonylation of Organic Nitro Compounds, Catalysis by Metal Complexes, Ugo, R. James, B. R., Eds. Kluwer, Dordrecht, The Netherlands, 1997. 

S. Cenini and F. Ragaini Catalytic Reductive Carbonylation of Organic Nitro Compounds. 1997 ISBN 0-7923 1307-7... 

Solid lithium aluminium hydride can be solublized in non-polar organic solvents with benzyltriethylammonium chloride. Initially, the catalytic effect of the lithium cation in the reduction of carbonyl compounds was emphasized [l-3], but this has since been refuted. A more recent evaluation of the use of quaternary ammonium aluminium hydrides shows that the purity of the lithium aluminium hydride and the dryness of the solvent are critical, but it has also been noted that trace amounts of water in the solid liquid system are beneficial to the reaction [4]. The quaternary ammonium aluminium hydrides have greater hydrolytic stability than the lithium salt the tetramethylammonium aluminium hydride is hydrolysed slowly in dilute aqueous acid and more lipophilic ammonium salts are more stable [4, 5]. 

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