Vanadium, sulfoxide complexes

The ability of vanadium(II) chloride to facilitate sulfoxide deoxygenation has been discussed (Section IV,C), and it appears that vana-dium(III) sulfoxide complexes may be prepared by air oxidation of van-adium(II) salts in the presence of the sulfoxide. In this manner, [V(Me2S0)6][C104]3 was prepared from vanadium(II) perchlorate (119) and the kinetics of substitution with thiocyanate ion detailed. Care is necessary in handling the pure compound, as it is reported to be sensitive to detonation. A large number of oxovanadium(IV) species have... 

Also, coordination compounds and metal carbonyls are able to undergo a PET, resulting in initiating radicals [63]. Recently investigated examples are iron chloride based ammonium salts [149], vanadium(V) organo-metallic complexes [150], and metal sulfoxide complexes [151]. However, the polymerization efficiency of some systems is only low due to redox reactions between the central metal ion and the growing polymer radical, and the low quantum yields of PET. 

The intermediate formed in this oxidation is 2 1 complex of SchifPs base ligand 7.62 and vanadium. This intermediate then reacts with hydrogen peroxide, eliminating one of the ligands to give a vanadium hydroperoxide complex, which then oxidizes the sulfide to sulfoxide. 

Vanadium(III) complexes, 473 adenine, 475 alcohols, 478 amides, 474, 480 amines, 474 amino acids, 484 ammonia, 474 aqua, 477 arsines, 476 azide, 475 bipyridyl, 475 bromides, 483 carboxylates, 479 catecholates, 478 chlorides, 482 complexones, 485 cyanides, 474,476 (Wethyl sulfoxide, 480 dioxygen, 478 dithiocarbamates, 481 dithiolates, 481 dithiophosphinates, 481 ethers, 478... 

VANADIUM(IV) COMPLEXES DERIVED EROM AROMATIC o-HYDROXYALDEHYDES AND TYROSINE DERIVATIVES CATALYTIC EVALUATION IN SULFOXIDATIONS... 

Bolm and Bienewald discovered in 1995 that some chiral vanadium (IV)-Schiff base complexes were efficient catalysts (1 mol %) for sulfoxidation [71a]. The catalyst 20 was prepared in situ by reacting VO(acac)2 with the Schiff base of a fJ-aminoalcohol (Scheme 6C.8). Reactions were conveniently performed in air at room temperature by slow addition of 1.1 mol equiv. of aqueous hydrogen peroxide (30%). Under these experimental conditions the reaction of methyl phenyl sulfide gave the corresponding sulfoxide in 94% yield and 70% ee. The best enantioselectivity was obtained in the formation of sulfoxide 21 (85% ee). Many structural analogues of catalyst 20 were screened for their efficacy, but none of... 

Since the oxidative polymerization of diphenyl disulfide catalyzed by VO(acac)2 results in selective formation of thioether bonds without any oxygenated compounds such as sulfoxides and/or sulfones, it should be noted that H20 should be produced predominantly by the reduction of 02 catalyzed by the vanadium complex without the formation of partially reduced side products such as H202. 

Vanadium(IV) Schiffsbase complexes derived from P-aminoalcohols 7.62 and vanadyl acetylacetonate have been used to oxidize different substrates to chiral sulfoxides. 

A number of metal / -diketonates have been used to catalyze the oxidation of sulfides to sulfoxides, important synthetic intermediates for the construction of various biologically active molecules . For example, an elegant study by Ishii and coworkers demonstrated that VO(acac)2 (35) selectively catalyzed the sulfoxidation of adamantane (41) by SO2/O2 to give 1-adamantane sulfonic acid (42) (equation 10) . Although a number of metal acac complexes were examined as catalysts for this reaction, all but the vanadium compound failed to promote the sulfoxidation. The catalytic oxidation of triarylphosphines using the palladium complex Pd(acac)2 (29) has also been investigated . 

In 1995, Bolm and Bienewald introduced a new, very practical method for the asymmetric catalytic oxidation of sulfides [44]. In the presence of vanadium complex prepared in situ from VO(acac)2 and 23 reactions of various sulfides or dithianes fike 24 with aqueous hydrogen peroxide afforded the corresponding sulfoxides with enantiomeric excesses of up to 85% (Eq. 2). Only traces of the corresponding sulfones were observed. The transformation can easily be carried out in open vessels at room temperature using inexpensive H2O2 as oxidant. 

Picolinic acid also accelerates the H2O2 oxidations but less efficiently than pyrazine-2-carboxylic acid. It has been demonstrated recendy that the vanadium complex with picolinic acid, VO(PA)2 , encapsulated into the NaY zeolite retains solution-like activity in the liquid-phase oxidation of hydrocarbons [16a], It is noteworthy that pyrazine-2-carboxylic acid accelerates the hydrocarbon oxidation catalyzed by CH3Re03 [25 b]. Employing a (+)-camphor derived pyrazine-2-carboxylic acid as a potential co-catalyst in the CHsReOj-catalyzed oxidation of methyl phenyl sulfide with urea-H202 adduct, the corresponding sulfoxide was obtained with an e.e. of 15% [16b]. 

In 1995, Bolm et al. reported that the vanadium complexes of the triden-tate and amino-acid derived ligands 15 catalyze the enantioselective sulfoxidation of prochiral thioethers with dihydrogen peroxide as the terminal oxidant (Scheme 8) (24). The ligands are synthesized by a one-step condensation of the readily available salicylic aldehydes 16 with amino-acid derived amino alcohols, such as 17a. 

Enantioselective sulfoxidation has been also studied using polymeric aminoalcohol-derived Schiff bases. Polymers 354-357 have been prepared by copolymeristation of the corresponding monomer with either MMA and EGDMA or styrene and DVB (Scheme 150) [219], These four polymers were then stirred with VO(acac)2 for 4h at rt to lead to the vanadium complexes. For the enantioselective oxidation of thioanisole, although the yields were similar to those obtained with the homogeneous analogs, the enantioselectivity were lower. The best selectivity was obtained with the catalyst derived from 355. 

An unusual electronic effect of substituents in the asymmetric oxidation of para-substituted thioanisoles and benzyl phenyl sulfide to sulfoxides, catalysed by the vanadium-Schiff base complexes (34), prepared from the synthesized enantiomers of Schiff bases, was observed. 

The most practical method that is used in the industrial synthesis of esomeprazole involves titanium-catalyzed oxidation with an alkyl hydroperoxide, and a dialkyltartrate as chiral ligand, in an organic solvent such as dichloromethane. A variety of oxidoreductases are known to catalyze the enantioselective oxidation of prochiral sulfides, usually as whole-cell biotransformations in aqueous media, but no simple metal complexes have been shown to be effective in water and the development of practical systems employing aqueous hydrogen peroxide as the primary oxidant is still an important challenge. In this context it is worth mentioning the enantioselective sulfoxidation of prochiral sulfoxides catalyzed by the semisynthetic peroxidase, vanadium-phytase, in an aqueous medium. 

Asymmetric sulfoxidation with chiral vanadium complexes is much older than Ti and A1 because this metal provides more robust catalysts which are not deactivated by the presence of water. The first contribution to the field was made by Bolm and co-workers in the second half of 1990s. These authors developed chiral catalysts formed in situ by the reaction of VO(acac)2 with chiral enantiopure Schiff ligands bearing one stereocenter based on a t-leucinol scaffold." The maximum ee achieved was 85% using low catalyst loadings (<1% mol) and without any precautions to avoid moisture or oxygen, which was unusual at that time as hydroperoxides... 

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