Scandium dodecyl sulfate

Scandium dodecyl sulfate has been used as a catalyst in an aqueous dispersion (6.19).66 The reaction was 5000 times faster in water than in methylene chloride. It was also slower in dimethyl sulfoxide, acetonitrile, ethyl ether, tetrahydrofuran, and methanol. 

Moreover, a new type of catalyst, scandium tris(dodecyl sulfate) [Sc(03S0Ci2H25)3,Sc(DS)3] has been developed.62. The catalyst (a Lewis Acid-Surfactant Combined Catalyst, LASC) acts both as a catalyst and as a surfactant, and aldol reactions proceed smoothly in the presence of a catalytic amount of Sc(DS)3 in water, without using any organic solvents (Scheme 16). 

With these results in hand, we have next introduced new types of Lewis acids, e.g scandium tris(-dodecyl sulfate) (4a) and scandium trisdodecanesul-fonate (5a) (Chart 1).[1S1 These Lewis acid-surfactant-combined catalysts (LASCs) were found to form stable colloidal dispersions with organic substrates in water and to catalyze efficiently aldol reactions of aldehydes with very water-labile silyl enol ethers. 

The surfactant-aided Lewis acid catalysis was first demonstrated in the model reaction shown in Table 13.1 [22]. While the reaction proceeded sluggishly in the presence of 10 mol% scandimn triflate (ScfOTOs) in water, a remarkable enhancement of the reactivity was observed when the reaction was carried out in the presence of 10 mol% Sc(OTf)3 in an aqueous solution of sodium dodecyl sulfate (SDS, 20 mol%, 35 mM), and the corresponding aldol adduct was obtained in high yield. It was found that the type of surfactant influenced the yield, and that Triton X-100, a non-ionic surfactant, was also effective in the aldol reaction (but required longer reaction time), while only a trace amount of the adduct was detected when using a representative cationic surfactant, cetyltrimethylammonium bromide (CTAB). The effectiveness of the anionic surfactant is attributed to high local concentration of scandium cation on the surfaces of dispersed organic phases, which are surroimded by the surfactant molecules. 

The results mentioned above prompted us to synthesize a more simplified catalyst, scandium tris(dodecyl sulfate) (Sc(DS)3) [23,24]. This new type of catalyst, Lewis acid-surfactant-combined catalyst (LASC) , was expected to act both as a Lewis acid to activate the substrate molecules and as a surfactant to form emulsions in water. Eng-berts and co-workers also reported a surfactant-type Lewis acid, copper bis(dodecyl sulfate) (Cu(DS)2) [25]. Although they studied detailed mechanistic aspects of Diels-Alder... 

As an extension of this study, a more simplified catalyst, scandium tris(dodecyl sulfate) (Sc(DS)3) has been developed (Scheme 12.62) [163]. 

It was shown that the Lewis acid surfactant-combined catalyst scandium tris(dodecyl sulfate) was an excellent catalyst for the aldol reaction in water without any organic cosolvent, providing yields up to The much higher activity observed in water than in organic... 

Kobayashi and coworkers showed that Lewis add surfactant-combined catalysts such as scandium tris(dodecyl sulfate), Sc(03SCi2H25)3, or copper bis(dodecyl sulfate), Cu(03SCi2H25)2, were efficient catalysts for the three-component Mannich-type reaction, with 73-95% yield being obtained in neat water.Neutral salts such as sodium triflate and sodium iodide catalyzed the condensation reaction in water between preformed imines and silicon enolates, or the three-component Mannich-type reaction using aromatic amines, with 49-93% yields and 0-80% diastereoselectivities. Mechanistic studies indicated that both sodium triflate and the Mannich adduct itself cooperatively promote the reaction. 

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