Title: The First Radical Method for the Introduction of an Ethynyl Group Using a Silicon Tether and Its Application to the Synthesis of 2‘-Deoxy-2‘-<i>C</i>-ethynylnucleosides<sup>1</sup>
Abstract: A novel radical method for the stereoselective introduction of an ethynyl group has been developed. When a solution of ethynyldimethylsilyl (EDMS) or [2-(trimethylsilyl)ethynyl]dimethylsilyl (TEDMS) ethers of trans-2-iodoindanol was treated with Et3B followed by tetrabutylammonium fluoride in toluene, atom transfer 5-exo-cyclization and subsequent elimination occurred to give cis-2-ethynylindanol in high yield. The method was shown to be useful in the introduction of an ethynyl group in various five- and six-membered-ring iodohydrins. Furthermore, 2'-deoxy-2'-C-ethynyluridine (6) and -cytidine (7), which were designed as novel antimetabolites, were readily synthesized by using this method as the key step. This would be the first example in which a radical reaction was used for introducing an ethynyl group.
Publication Year: 2003
Publication Date: 2003-04-09
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
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Cited By Count: 45
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