Reaction polarity reversal catalysis

Reagent for Polarity Reversal Catalysis in Radical Reactions. Polarity reversal catalysis (PRC) has been established by Roberts in free-radical chemistry as an efficient alternative to the use of stannanes (e.g., tri-/>butylstannane) and their associated toxicity and purification problems. Silyl radicals can be a valid alternative to tin radicals for one of the most common radical reactions, that is, radical dehalogenation, but silanes, contrary to stannanes, cannot sustain an effective radical chain reaction, due to the stronger Si-H bond. 

The low reactivity of alkyl and/or phenyl substituted organosilanes in reduction processes can be ameliorated in the presence of a catalytic amount of alkanethiols. The reaction mechanism is reported in Scheme 5 and shows that alkyl radicals abstract hydrogen from thiols and the resulting thiyl radical abstracts hydrogen from the silane. This procedure, which was coined polarity-reversal catalysis, has been applied to dehalogenation, deoxygenation, and desulfurization reactions.For example, 1-bromoadamantane is quantitatively reduced with 2 equiv of triethylsilane in the presence of a catalytic amount of ferf-dodecanethiol. 

A majority of radical addition occurs with electron-poor alkenes using alkyl halides in the presence of BusSnH. These reactions are feasible due to a proper matching between the radical acceptor and the donor. However, when the alkene is electron-rich and since simple alkyl radicals are considered as nucleophilic, the reaction is not a practical method for carbon-carbon bond formation. By applying the concept of polarity-reversal catalysis, an additional reagent is introduced which alleviates the mismatch between the partners and makes the reaction feasible. A few examples illustrating this concept have been described in this review. 

The reaction of thiyl radicals with silicon hydrides (Reaction 3.18) is the key step of the so called polarity-reversal catalysis in the radical-chain reduction of alkyl halides as well as in the hydrosilylation of olefins using silane-thiol couple (see Sections 4.5 and 5.1) [33]. The reaction is strongly endothermic and reversible (Reaction —3.18). 

The addition of silanes across alkenes has been investigated both experimentally145 and theoretically.146 The effect of optically active thiol catalysts to catalyse radical hydrosilylation (polarity reversal catalysis) has been studied. The use of 2,3,4,6-tetra-O-acetyl-thio-jS-D-glucopyranose as the chiral thiol (used to reduce the intermediate carbon-based radicals) furnished the hydrosilylated alkenes in low to moderate enantiomeric excesses.145 In addition to this work a theoretical study on the reactions of SiH3 with ethene and propene has been undertaken using PMP2(6-31G ) and QCISD(T)(6-31G ) methods. Results indicated that the alkene-addition pathway is favoured over the alternative possible mode of reaction (H-abstraction). This is contrary to that previously suggested for the reaction of SiF with propene.146... 

Phenylselenyl radicals are also formed when benzeneselenol is used as a reducing agent. These radicals are usually unable to propagate chain reactions since they dimerize rapidly. Two important exceptions are known the propagation with acyl thiohydroxamates ( Barton esters ) and the use of polarity reversal catalysis. 

Polarity-reversal catalysis of hydrogen-atom abstraction reactions concepts and applications in organic chemistry. 

Polarity-reversal catalysis has been used to mediate a cyclization reaction that otherwise could not be accomplished." Reaction of (31) with the peroxide (32) failed to produce any of the desired cyclic material (33). However, when the reaction was repeated in the presence of tri-r-butoxysilathiol (5 mol%) as a polarity-reversal catalyst, the cyclic compound (33) was furnished in 92% yield (Scheme 17)." ... 

Thiol-catalyzed Radical-chain Cyclization of Unsaturated Acetals and Thioacetals. When the unsaturated dioxolane 1 and a radical initiator, 2,2-di(t-butylperoxy)butane (DBPB), were heated at 125 °C in octane in the presence of tri(f-butoxy) silanethiol (TBST), the spirocyclic ketal 2 was formed cleanly and isolated in 92% yield (eq 1). When the reaction was performed in the absence of TBST, compound 2 was not detected. TBST is believed to promote the generation of the l,3-dioxolan-2-yl radical 3 by hydrogen-atom abstraction from 1 in a process termed polarity-reversal catalysis (eq 2). 

The exchange reaction of 1-bromonaphthalene with CuCl proceeds effectively in polar solvents, such as DMF or DMSO, at temperatures of 110-150 °C via a second-order mechanism. The reaction is reversible but the equilibrium favors formation of aryl chlorides. The catalysis is inhibited by chloride anion and by pyridine or, particularly, 2,2 -bipyri-dine. The ease of replacement decreased in the order Arl> ArBr> ArCl and the reactivity of the attacking nucleophile decreased in the order CuCl> CuBr> Cul. The exchange reac-... 

Solubilization, Microemulsions and Emulsions. - Micellar solutions with both normal (Li) and reverse (L2) curvature, e.g. o/w and w/o type systems, can be swollen by oil and water to obtain water/oil/amphiphile ternary or pseudoternary systems. These systems have been widely used as solubilizing media for structural investigations of the immobilized solubilizate (a protein for instance), for drug delivery systems, and also for reaction media, (micellar catalysis). Ternary systems based on water, oil, and amphiphile mixtures can form a variety of Li and L2 monophasic regions. When these systems form isotropic solutions spontaneously, they are termed microemulsions. The formation of a microemulsion is related mainly to a substantial decrease of the interfacial tension (Yo/w) at the oil-water interface, due to the amphiphilic molecules located at the polar-apolar interface. This occurs in agreement with the typical equation ... 

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