期刊
PURE AND APPLIED CHEMISTRY
卷 72, 期 7, 页码 1327-1334出版社
WALTER DE GRUYTER GMBH
DOI: 10.1351/pac200072071327
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Neurotoxic organotin reagents currently play a key role in radical chemistry. As a result, this is an important area for development of new clean replacement reactions. The pharmaceutical industry in particular has had to avoid use of radical methodology for the formation of carbon-carbon bonds for this reason. With the current dawn in green chemistry, a host of new clean radical methods is beginning to flourish. Our aim has been to develop new nontoxic methodology for carbon-carbon bond formation by radical chemistry, which would provide either reductive termination (giving a hydrogen atom to the ultimate radical, as happens with tributyltin hydride), or oxidative functionalization, installing a useful polar group at the site of the ultimate radical. Two methods for effecting radical reactions in an environmentally friendly way are presented: (i) The tetrathiafulvalene (TTF)-mediated radical-polar crossover reaction converts arenediazonium salts to aryl radicals, which have sufficient lifetime to cyclize onto alkenes-the resulting alkyl radicals couple with TTF+. to afford sulfonium salts which, in turn, undergo solvolysis to alcohols, ethers or amides. The method provides the key step in a synthesis of (+/-)-aspidospermidine. (ii) Hypophosphite salts and hypophosphorous acid, on the other hand, form C-C bonds with reductive termination. These economical reagents afford radicals efficiently, starting from aryl iodides, alkyl bromides, and alkyl iodides, and give very easy separation of products from by-products.
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