Titanium, sulfoxide complexes

A review on the chemistry of low-valent titanium has appeared which deals with some aspects of the chemistry of titanium sulfoxide complexes (397). Titanyl complexes of the type [Ti0L5][C104]2 have... 

The patent literature contains several references to the use of sulfoxide complexes, usually generated in situ, as catalyst precursors in oligomerization and polymerization reactions. Thus, a system based upon bis(acrylonitrile)nickel(0> with added Me2SO or EtgSO is an effective cyclotrimerization catalyst for the conversion of butadiene to cyclo-1,5,-9-dodecatriene (44). A similar system based on titanium has also been reported (407). Nickel(II) sulfoxide complexes, again generated in situ, have been patented as catalyst precursors for the dimerization of pro-pene (151) and the higher olefins (152) in the presence of added alkyl aluminum compounds. 

In the same year, Fujita s group63 reported the asymmetric oxidation of aryl methyl sulfide by hydroperoxides (TBHP, CHP) and an optically active catalyst formed by a Schiff base-oxovanadium(IV) complex 32, giving (S)-sulfoxides in low ee (up to 40%) (Fig. 4). Later, they developed64 a more promising approach using 33, a binuclear Schiff base-titanium(IV) complex (4 mol% equiv) to catalyze the asymmetric oxidation of methyl phenyl sulfide by trityl hydroperoxide in methanol at 0 °C. The (ft)-methyl phenyl sulfoxide was obtained with 60% ee. 

The use of ionic liquids to perform asymmetric sulfoxidation reactions was proposed by Halligudi and coworkers. A chiral titanium-BINOL complex was immobilised onto ionic liquid-modified mesoporous silica (SBA-15) support 14 and the resulting heterogeneous catalyst was successfully employed in asymmetric sulfoxidation of thioanisole using TBHP as... 

Another asymmetric sulfoxidation reported by Fujita et al. [102] used a chiral binuclear titanium(IV) complex (4 mol% equiv) in methanol with trityl hydroperoxide at 0°C, which gave methyl phenyl sulfoxide with an ee of 53% and a good yield (87%). The complex was prepared by treating TiC in pyridine with -disalicylidene-(f ,/ )-l,2-cyclohexanediamine. The structure of the catalyst was determined by x-ray analysis. A binuclear titanium (IV) complex was present with an oxygen bridge between the two titanium atoms (Ti—O— Ti unit). This oxygen apparently comes from atmospheric or solvent moisture. Each titanium atom is octahedrally coordinated, and the planes of each titanium atom with its associated Schiff bases are almost parallel to each other. 

Uemura et al. [103] developed an efficient catalytic and enantioselective oxidation of prochiral sulfides. As in the Kagan system, a titanium(IV) complex is produced in situ from a titanium alkoxide and two / -(-F)-binaphthols (Scheme 1.12) as chiral auxiliaries (in place of diethyl tartrate), in the presence of a large amount of water (more than 1 equivalent). The oxidation of methyl p-tolyl sulfide gives the corresponding sulfoxide in 45 h in 90% yield and 73% ee. 

Fujita et al. used a catalytic amount of a binuclear titanium(IV) complex in an attempt to find an efficient system to oxidize sulfides with high enantioselectivity [102]. Prior to this study, they investigated other systems with several transition metals. A similar asymmetric sulfoxidation was discovered [105] using a catalytic amount of nonracemic Schiff base oxovanadium complex (Table 1.4) under atmospheric conditions at room temperature in dichloromethane. With 0.1 mol% of catalyst and cumene hydroperoxide as oxidant, oxidation produces sulfoxides in excellent yields. However, the reaction is limited to alkyl aryl sulfide substrates, and the best enantioselectivity obtained was 40% ee, for (S)-methyl p-methoxy phenyl sulfoxide. 

Bearing these considerations in mind, Reddy and Verkade prepared a titanium alkoxide complex, 72, with good stability toward moisture for the selective oxidation of sulfides to sulfones and sulfoxides with hydrogen peroxide in recyclable ionic liquid solvents at room temperature [56]. They optimized reaction conditions and recovering procedure for thioanisole 71, and used their obtained results for oxidation of different aliphatic, aromatic and xmsaturated sulfides. Their results proved the chemoselectivity... 

Colona and coworkers oxidized a variety of alkyl aryl and heterocyclic sulfides to the sulfoxides using t-butyl hydroperoxide and a catalytic amount of a complex (97) derived from a transition metal and the imines of L-amino acids. Of the metals (M = TiO, Mo02, VO, Cu, Co, Fe), titanium gave the highest e.e. (21%), but molybdenum was the most efficient catalyst. The sulfoxides were accompanied by considerable sulfone125. 

Recently, Feng and co-workers reported an asymmetric sulfide oxidation" catalyzed by titanium complexes bearing HydrOx ligands, for example, 576 (Scheme 8.199). ° Enantioselectivities approached a level of synthetic utility for oxidation of aryl alkyl sulfides 632 although the yields of the sulfoxide 633 were poor due to overoxidation to the sulfone 634. The overoxidation is especially significant for reactions with high enantioselectivity. 

Oxidation of the enantiotopic electron pairs at sulfur, mediated by chiral titanium complexes, to yield chiral sulfoxides with high enantiomeric excess14. 

The complications which result from the hydrolysis of alkali metal cyanides in aqueous media may be avoided by the use of non-aqueous solvents. The one most often employed is liquid ammonia, in which derivatives of some of the lanthanides and of titanium(III) may be obtained from the metal halides and cyanide.13 By addition of potassium as reductant, complexes of cobalt(O), nickel(O), titanium(II) and titanium(III) may be prepared and a complex of zirconium(0) has been obtained in a remarkable disproportion of zirconium(III) into zirconium(IV) and zirconium(0).14 Other solvents which have been shown to be suitable for halide-cyanide exchange reactions include ethanol, methanol, tetrahydrofuran, dimethyl sulfoxide and dimethylformamide. With their aid, species of different stoichiometry from those isolated from aqueous media can sometimes be made [Hg(CN)3], for example, is obtained as its cesium salt form CsF, KCN and Hg(CN)2 in ethanol.15... 

The Orsay group found serendipitously that methyl p-tolyl sulfide was oxidized to methyl p-toly 1 sulfoxide with high enantiomeric purity (80-90% ee) when the Sharpless reagent was modified by addition of 1 mole equiv. of water [16,17]. The story of this discovery was described in a review [19], Sharpless conditions gave racemic sulfoxide and sulfone. Careful optimization of the stoichiometry of the titanium complex in the oxidation of p-tolyl sulfide led to the selection of Ti(0iPr)4/(7 ,7 )-DET/H20 (1 2 1) combination as the standard system [ 17]. In the beginning of their investigations, the standard conditions implied a stoichiometric amount of the chiral titanium complex with respect to the prochiral sulfide [16,17,20-23]. Later, proper conditions were found, which decreased the amount of the titanium complex without too much alteration of the enantioselectivity [24,25],... 

Uemura et al. [49] found that (R)-1,1 -binaphthol could replace (7 ,7 )-diethyl tartrate in the water-modified catalyst, giving good results (up to 73% ee) in the oxidation of methyl p-tolyl sulfoxide with f-BuOOH (at -20°C in toluene). The chemical yield was close to 90% with the use of a catalytic amount (10 mol %) of the titanium complex (Ti(0-i-Pr)4/(/ )-binaphthol/H20 = 1 2 20). They studied the effect of added water and found that high enantioselectivity was obtained when using 0.5-3.0 equivalents of water with respect to the sulfide. In the absence of water, enantioselectivity was very low. The beneficial effect of water is clearly established here, but the amount of water needed is much higher than that in the case of the catalyst with diethyl tartrate. They assumed that a mononuclear titanium complex with two binaphthol ligands was involved, in which water affects the structure of the titanium complex and its rate of formation. 

Reetz et al. [53] prepared analogues of (R)-binol as ligands for the titanium complex in the presence of water under the same conditions as Uemura s mentioned above. In this study, (R)-octahydrobinol and its dinitro derivative were synthesized. The reaction using (R)-dinitro-octahydrobinol ligand gave (. S j-methyl p-tolyl sulfoxide (86% ee) [53], which makes a sharp contrast to the reaction using (R)-binol wherein (A1 (-methyl p-tolyl sulfoxide was formed [50]. It is probable that kinetic resolution is involved, giving some asymmetric amplification. 

Uemura reported a highly enantioselective oxidation of sulfides to sulfoxides using a chiral titanium complex prepared from chiral BINOL and Ti(0-i-Pr)4, and this reaction exhibits a remarkable asymmetric amplification (Scheme 9.15) [33]. 

An irreversible tt-ct rearrangement has been observed to occur with the treatment of titanocene dicloride (8) with dimethyl sulfoxide (17). The o complex (9) has been isolated, however, treatment of the reaction mixture with benzene produces the titanium complex of dimethyl sulfoxide (10), and treatment of the reaction mixture with maleic anhydride produces the cyclopentadiene addition product (11). Monitoring the reaction mixture by proton NMR spectroscopy demonstrates the ir-a change in the bonding of the cyclopentadienyl ligands. 

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