Reduction xanthates

Sodium Borohydride Reduction of Ethyl 5a.-Cholestan-3-one 2a.-Xanthate ... 

Substitution at the SiH moiety has been carried out with alkylthio groups, such as MeS and i-PrS. Tn s(alkylthio)silanes, (RSlsSiH, are radical-based reducing agents which can effect the reduction of bromides, iodides, xanthates, phenylselenides, and isocyanides in toluene, using AIBN as the initiator at 85... 

Xanthate compounds are widely used as collectors in flotation. Their function is to render the mineral surface hydrophobic and thus facilitate bubble attachment. The adsorption of xanthates onto sulfide minerals occurs via an electrochemical mechanism involving the reduction of oxygen and the anodic adsorption of xanthate. 

Scheme 5.9 illustrates some of the conditions that have been developed for the reductive deoxygenation of alcohols. Entries 1 to 4 illustrate the most commonly used methods for generation of thiono esters and their reduction by tri-M-butylstannane. These include formation of thiono carbonates (Entry 1), xanthates (Entry 2), and thiono imidazolides (Entries 3 and 4). Entry 5 is an example of use of dimethyl phosphite as the hydrogen donor. Entry 6 uses r .s-(trimethylsilyl)silane as the hydrogen atom donor. 

N-Ethylpiperidi 11 i um hypophosphite has been used as a reductant in deoxygenation of nucleoside diol xanthates in aqueous solution.300... 

The electrochemical mechanism can be well explained with the mineral pyrite. The collector ion is xanthate ion (CT), a member in the anodic sulfydryl collectors group. Two electrochemical reactions occur on the surface of the pyrite. There is the formation of dixanthogen (C2) by anodic oxidation of xanthate ion (CT) on the surface of pyrite coupled with cathodic reduction of adsorbed oxygen. These reactions are shown below ... 

A Sml2-induced reductive cyclization of (V-(alkylketo)pyrroles provided an entry into medium ring 1,2-annelated pyrroles <06EJO4989>. An oxidative radical alkylation of pyrroles with xanthates promoted by triethylborane provided access to a-(pyrrol-2-yl)carboxylic acid derivatives <06TL2517>. An oxidative coupling of pyrroles promoted by a hypervalent iodine(III) reagent provided bipyrroles directly <060L2007>. 

Wood [127] reported an innovative development of the Barton-McCombie deoxygenation of alcohols allowed to work under tin-free conditions. A trimethylborane-water complex proves to be an efficient reagent for the reduction of xanthates. Complexation of water by trimethylborane induces a strong decrease of O - H bond dissociation energy from 116 kcal/mol (water) to 86 kcal/mol (Me3B-water complex). 

The mixed-potential model demonstrated the importance of electrode potential in flotation systems. The mixed potential or rest potential of an electrode provides information to determine the identity of the reactions that take place at the mineral surface and the rates of these processes. One approach is to compare the measured rest potential with equilibrium potential for various processes derived from thermodynamic data. Allison et al. (1971,1972) considered that a necessary condition for the electrochemical formation of dithiolate at the mineral surface is that the measmed mixed potential arising from the reduction of oxygen and the oxidation of this collector at the surface must be anodic to the equilibrium potential for the thio ion/dithiolate couple. They correlated the rest potential of a range of sulphide minerals in different thio-collector solutions with the products extracted from the surface as shown in Table 1.2 and 1.3. It can be seen from these Tables that only those minerals exhibiting rest potential in excess of the thio ion/disulphide couple formed dithiolate as a major reaction product. Those minerals which had a rest potential below this value formed the metal collector compoimds, except covellite on which dixanthogen was formed even though the measured rest potential was below the reversible potential. Allison et al. (1972) attributed the behavior to the decomposition of cupric xanthate. 

According to the mixed potential theory, an anodic reaction can occur only if there is a cathodic reaction proceeding at finite rate at that potential (Rand and Woods, 1984). For the flotation systems, the cathodic reaction is usually given by the reduction of oxygen. The corresponding anodic reaction involves interaction of xanthate on the sulphide minerals in various ways, including the reaction of xanthate with the sulphide mineral (MS) to form metal xanthate and the oxidation of xanthate to dixanthogen (X2) at the mineral surface. 

A relevant reductive process, which has found wide application in organic synthesis, is the deoxygenation of alcohols introduced in 1975 by Barton and McCombie [58]. Reaction (4.28) shows that the thiocarbonyl derivatives, easily obtained from the corresponding alcohol, can be reduced in the presence of BusSnH under free radical conditions. The reactivity of xanthates and thiocarbonyl imidazolides [58] was successfully extended to 0-arylthiocarbonates [59] and (9-thioxocarbamates [60]. Several reviews have appeared on this subject, thus providing an exhaustive view of this methodology and its application in natural product synthesis [61-64]. 

Cyclohexyl xanthate has been used as a model compound for mechanistic studies [43]. From laser flash photolysis experiments the absolute rate constant of the reaction with (TMS)3Si has been measured (see Table 4.3). From a competition experiment between cyclohexyl xanthate and -octyl bromide, xanthate was ca 2 times more reactive than the primary alkyl bromide instead of ca 50 as expected from the rate constants reported in Tables 4.1 and 4.3. This result suggests that the addition of silyl radical to thiocarbonyl moiety is reversible. The mechanism of xanthate reduction is depicted in Scheme 4.3 (TMS)3Si radicals, initially generated by small amounts of AIBN, attack the thiocarbonyl moiety to form in a reversible manner a radical intermediate that undergoes (3-scission to form alkyl radicals. Hydrogen abstraction from the silane gives the alkane and (TMS)3Si radical, thus completing the cycle of this chain reaction. 

The reduction of thiocarbonyl derivatives by EtsSiH can be described as a chain process under forced conditions (Reaction 4.50) [89,90]. Indeed, in Reaction (4.51) for example, the reduction of phenyl thiocarbonate in EtsSiD as the solvent needed 1 equiv of dibenzoyl peroxide as initiator at 110 °C, and afforded the desired product in 91 % yield, where the deuterium incorporation was only 48% [90]. Nevertheless, there are some interesting applications for these less reactive silanes in radical chain reactions. For example, this method was used as an efficient deoxygenation step (Reaction 4.52) in the synthesis of 4,4-difluoroglutamine [91]. 1,2-Diols can also be transformed into olefins using the Barton-McCombie methodology. Reaction (4.53) shows the olefination procedure of a bis-xanthate using EtsSiH [89]. 

Other silanes have been used as mediators in the intermolecular C—C bond formation. They can be used alone, as in the following example of the disilane (Ph2SiH)2 shown in Reaction (7.6), for the reductive addition of a bromide or a xanthate to phenyl vinyl sulfone [11,12]. 

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