Reductive alkylation sulfur functionality

Sulfur Substituents. Acetylation and alkylation of pyridinethiones usually take place on sulfur (39). An exception to this is 4-pyridinethione [19829-29-9] which is acetylated on nitrogen. Displacement of thioethers can be achieved with hydroxide or amines (eq. 13) (40). Thioether functional groups can also be removed by reduction (39). 

Dimsylsodium (24) functions as a highly basic sulfur ylide. It can be used to convert phosphonium salts to phosphorus ylides for use in the Wittig reaction. Dimsylsodium also reacts with aldehydes and ketones by nucleophilic addition to form epoxides and with esters by nucleophilic substitution to yield p-ketosulfoxides (25) (Scheme 11). The p-ketosulfoxides (25) contain acidic a-hydrogens which can be readily removed to allow alkylation, and the products (26) suffer reductive desulfuration on treatment with aluminium amalgam to yield ketones (27) (Scheme 11) This procedure can, for instance, be applied to the conversion of ethyl benzoate to propiophenone (28) (Scheme 12). 

The sulfone is a versatile functional group comparable to the carbonyl functionality in its ability to activate molecules for further bond construction, the main difference between these two groups being that the sulfone is usually removed once the synthetic objective is achieved. The removal most commonly involves a reductive desulfonylation process with either replacement of the sulfone by hydrogen (Eq. 1), or a process that results in the formation of a carbon-carbon multiple bond when a P-functionalized sulfone, for example a (3-hydroxy or (3-alkoxy sulfone, is employed (Eq. 2). These types of reactions are the Julia-Lythgoe or Julia-Paris-Kocienski olefination processes. Alkylative desulfonylation (substitution of the sulfone by an alkyl group, Eq. 3), oxidative desulfonylation (Eq. 4), and substitution of the sulfone by a nucleophile (nucleophilic displacement, Eq. 5) are also known. Finally, p-eliminations (Eq. 6) or sulfur dioxide extrusion processes (Eqs. 7, 8 and 9) have become very popular for the... 

Chiral sulfoxides have been extensively employed as asymmetric auxiliary group that assist stereoselective reactions. The sulfoxide functional group activates adjacent carbon-hydrogen bonds to allow proton abstraction by bases, and the corresponding anions can be alkylated [1176] oracylated [1177] with high diastereo-selectivity. Similarly, thermal elimination [1178] and reduction of a-keto sulfoxides [1179] can proceed with transfer of chirahty from sulfur to carbon. In spite of... 

A number of phase transfer reactions of sulfur containing substrates have been reported. These include substitution reactions in which sulfur is nucleophile, electrophile or an ancillary function. The synthesis of a variety of thioethers has been reported, as have the alkylation of numerous sulfur stabilized carbanions. In addition, reduction of both disulfides and N-tosylsulfilimines have been conducted under phase transfer catalytic conditions. The unifying theme of this chapter is, therefore, the synthesis and reactions of sulfur containing molecules. Inherent in this approach is some redundancy, but it is hoped that the ability to locate reactions of interest compensates. 

Graphite reacts with alkali metals - potassium, cesium and rubidium - to form lamellar compounds with different stoichiometries. The most widely known intercalate is the potassium-graphite which has the stoichiometry of CgK. In this intercalate the space between the graphite layers is occupied by K atoms. CgK functions as a reducing agent in various reactions such as reduction of double bonds in a,fl-unsaturated ketones [19], carboxylic acids and Schiff bases alkylation of nitriles [20], esters and imines [21] reductive cleavage of carbon-sulfur bonds in vinylic and allylic sulfones [22]. The detailed reaction mechanism of CgK is not known, and the special properties which are ascribed to the intercalate come either from the equilibrium between K+/K [23], or topochemical observations (the layer structure) [24]. 

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