Reduction phenylselenides

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... 

Tris[(2-perfluorohexyl)ethyl]tin hydride has three perfluorinated segments with ethylene spacers and it partitions primarily (> 98%) into the fluorous phase in a liquid-liquid extraction. This feature not only facilitates the purification of the product from the tin residue but also recovers toxic tin residue for further reuse. Stoichiometric reductive radical reactions with the fluorous tin hydride 3 have been previously reported and a catalytic procedure is also well established. The reduction of adamantyl bromide in BTF (benzotrifluoride) " using 1.2 equiv of the fluorous tin hydride and a catalytic amount of azobisisobutyronitrile (AIBN) was complete in 3 hr (Scheme 1). After the simple liquid-liquid extraction, adamantane was obtained in 90% yield in the organic layer and the fluorous tin bromide was separated from the fluorous phase. The recovered fluorous tin bromide was reduced and reused to give the same results. Phenylselenides, tertiary nitro compounds, and xanthates were also successfully reduced by the fluorous fin hydride. Standard radical additions and cyclizations can also be conducted as shown by the examples in Scheme 1. Hydrostannation reactions are also possible, and these are useful in the techniques of fluorous phase switching. Carbonylations are also possible. Rate constants for the reaction of the fluorous tin hydride with primary radicals and acyl radicals have been measured it is marginally more reactive than tributlytin hydrides. ... 

Other heteroatomic bond cleavages have found synthetic applications. One of these is the reduction of diphenyldiselenide by sodium under irradiation at 50 kHz, giving sodium phenylselenide (Eq. 30, see p. 371).1 8... 

Pyirolidine-fused systems of type 88 (R=Me, Et, Pfi, Bn) have been made by cyclization of a radical at C-2 (from reduction of a phenylselenide) onto an allylic amine at C-3 analogous chemistiy in which the positicms of the amine and the PhSe group were reversed led to the systems with the pyrrolidine fused in the opposite sense. Good endo-selectivity was observed in the case of 88, but the regioisomer was formed with lower endo) selectivity,... 

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