Ketone-metal complexes

Reactions 33 and 35 constitute the two principal reactions of alkyl hydroperoxides with metal complexes and are the most common pathway for catalysis of LPOs (2). Both manganese and cobalt are especially effective in these reactions. There is extensive evidence that the oxidation of intermediate ketones is enhanced by a manganese catalyst, probably through an enol mechanism (34,96,183—185). 

Condensation of vinyl chloride with formaldehyde and HCl (Prins reaction) yields 3,3-dichloro-l-propanol [83682-72-8] and 2,3-dichloro-l-propanol [616-23-9]. The 1,1-addition of chloroform [67-66-3] as well as the addition of other polyhalogen compounds to vinyl chloride are cataly2ed by transition-metal complexes (58). In the presence of iron pentacarbonyl [13463-40-6] both bromoform [75-25-2] CHBr, and iodoform [75-47-8] CHl, add to vinyl chloride (59,60). Other useful products of vinyl chloride addition reactions include 2,2-di luoro-4-chloro-l,3-dioxolane [162970-83-4] (61), 2-chloro-l-propanol [78-89-7] (62), 2-chloropropionaldehyde [683-50-1] (63), 4-nitrophenyl-p,p-dichloroethyl ketone [31689-13-1] (64), and p,p-dichloroethyl phenyl sulfone [3123-10-2] (65). 

The second type is comprised of 2 1 metal complexes of OjO -dihydroxy azo dyes which generally do not contain sulfo or other strongly hydrated groups as found ia the premetallized 2 1 complexes for wool. Thus their solubiUty ia esters, ketones, and alcohols is relatively iacreased. Cl Solvent Violet 1... 

Acid Dyes. These water-soluble anionic dyes ate appHed to nylon, wool, sUk, and modified acryHcs. They ate also used to some extent for paper, leather, food, and cosmetics. The original members of this class aU had one or mote sulfonic or catboxyHc acid groups in thein molecules. This characteristic probably gave the class its name. Chemically, the acid dyes consist of azo (including preformed metal complexes), anthraquiaone, and ttiaryHnethane compounds with a few azHie, xanthene, ketone imine, nitro, nitroso, and quHiophthalone compounds. 

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... 

A unique method to generate the pyridine ring employed a transition metal-mediated 6-endo-dig cyclization of A-propargylamine derivative 120. The reaction proceeds in 5-12 h with yields of 22-74%. Gold (HI) salts are required to catalyze the reaction, but copper salts are sufficient with reactive ketones. A proposed reaction mechanism involves activation of the alkyne by transition metal complexation. This lowers the activation energy for the enamine addition to the alkyne that generates 121. The transition metal also behaves as a Lewis acid and facilitates formation of 120 from 118 and 119. Subsequent aromatization of 121 affords pyridine 122. 

In the above cases, an optically active reducing agent or catalyst interacts with a prochiral substrate. Asymmetric reduction of ketones has also been achieved with an achiral reducing agent, if the ketone is complexed to an optically active transition metal Lewis acid. ... 

Similar transformations have been performed with Danishefsky s diene and glyoxylate esters [85] catalyzed by bis (oxazoHne)-metal complexes to afford the hetero Diels-Alder product in 70% isolated yield and up to 72% ee. Jorgensen [86,87] reported a highly enantioselective, catalytic hetero Diels-Alder reaction of ketones and similar chiral copper(II) complexes leading to enantiomeric excesses up to 99% (Scheme 31, reaction 2). They also described [88] a highly diastereo- and enantioselective catalytic hetero Diels-Alder reaction of /I, y-imsaturated a-ketoesters with electron-rich alkenes... 

Employing ketones or aldehydes as starting materials, the corresponding silylethers are obtained. Thereafter, the oxidation or hydrolysis of the obtained silylethers gives the corresponding alcohols (Scheme 17). In most cases, a hydride (silyl) metal complex H-M-Si (M = transition-metal), which is generated by an oxidative addition of H-Si bond to the low-valent metal center, is a key intermediate in the hydrosilylation reaction. 

Graddon, D. P. (1968). Divalent transition metal j8-ketone-enolate complexes as Lewis acids. Coordination Chemistry Reviews, 4, 1-28. 

Hok, B., Studies on the extraction of metal complexes. XV. The dissociation constants of salicylic acid, 3,5-dinitrobenzoic acid, and cinnamic acid and the distribution between chloroform-water and methyl isobutyl ketone (hexone)-water, Sv. Kem. Tidskr. 65, 182-194 (1953). 

Enantiometrically pure alcohols are important and valuable intermediates in the synthesis of pharmaceuticals and other fine chemicals. A variety of synthetic methods have been developed to obtain optically pure alcohols. Among these methods, a straightforward approach is the reduction of prochiral ketones to chiral alcohols. In this context, varieties of chiral metal complexes have been developed as catalysts in asymmetric ketone reductions [ 1-3]. However, in many cases, difficulties remain in the process operation, and in obtaining sufficient enantiomeric purity and productivity [2,3]. In addition, residual metal in the products originating from the metal catalyst presents another challenge because of the ever more stringent regulatory restrictions on the level of metals allowed in pharmaceutical products [4]. An alternative to the chemical asymmetric reduction processes is biocatalytic transformation, which offers... 

The Schiff bases being derivatives of aldehydes or ketones and various amines have received considerable attention because of their interesting physical and chemical properties, involvement in biologically important reactions and widespread application of their metal complexes. Increasing interest in optically active Schiff bases is connected with the discovery at the beginning of the 1990s of the so-called Jacobsen catalysts used in several asymmetric reactions showing excellent enantioselectivity. 

Aliphatic ketone, methylene function reduction, 6-phenylhex-l-ene, 131-132 Alkane reduction alcohols, 12-27 allyl alcohols, 24 benzyl alcohols, 18-24 cyclopropylcarbinols, 17-18 metal-complexed alcohols,... 

The efficiency of the extraction depends on the coordinating ability of the solvent, and on the acidity of the aqueous solution which determines the concentration of the metal complex. Coordinating ability follows the sequence ketones > esters > alcohols > ethers. Many metals can be extracted as fluoride, chloride, bromide, iodide or thiocyanate complexes. Table 4.5 shows how the extraction of some metals as their chloro complexes into diethyl ether varies with acid concentration. By controlling... 

Bonne, J. R., Reduction of Cyclic and Bicyclic Ketones by Complex Metal Hydrides, 11, 53. Bonner, W. A., Origins of Chiral Homogeneity in Nature, 18, 1. 

As documented throughout this handbook, the diversity of reaction patterns of transition-metal complexes leads to a remarkably rich chemistry, with a tremendous mechanistic diversity in the details of how H2 is added to unsaturated substrates. Over forty years ago, Walling and Bollyky reported a catalytic hydrogenation of benzophenone that required no transition metal at all They found that the C=0 bond of benzophenone can be catalytically hydrogenated using KOtBu as a base [88], but harsh conditions (200°C, 100 bar H2) were used (Eq. (49)). Ber-kessel et al. recently examined details of this reaction and provided evidence that it was first order in ketone, first order in hydrogen, and first order in base [89]. 

In summary, the reduction of ketones and aldehydes can both be performed with MPV and transition-metal complexes as catalysts. Reductions of alkenes, al-kynes, and imines require transition-metal catalysts MPV reductions with these substrates are not possible. 

Cyanohydrination (addition of a cyano group to an aldehyde or ketone) is another classic reaction in organic synthesis. Enantioselective addition of TMSCN to aldehyde, catalyzed by chiral metal complexes, has also been an active area of research for more than a decade. The first successful synthesis using an (5,)-binaphthol based complex came from Reetz s group142 in 1986. Their best result, involving Ti complex, gave 82% ee. Better results were reported shortly thereafter by Narasaka and co-workers.143 They showed that by... 

In summary, many attempts have been made at achieving enantioselective reduction of ketones. Modified lithium aluminum hydride as well as the ox-azaborolidine approach have proved to be very successful. Asymmetric hydrogenation catalyzed by a chiral ligand-coordinated transition metal complex also gives good results. Figure 6-7 lists some of the most useful chiral compounds relevant to the enantioselective reduction of prochiral ketones, and interested readers may find the corresponding applications in a number of review articles.77,96,97... 

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