Synthesis of chiral cyclohexanes and carbasugars by 6-exo-dig radical cyclisation reactions

Treatment of 5-(tert-butyldimethylsilyl)-2,3-O-isopropylidene-D-ribose with lithium acetylides gave mixtures of syn- and anti-alkynols 2a-2c which were separated following protection as methoxymethyl ethers. These were converted to the corresponding iodides which underwent 6-exo-dig radical cyclisation to afford chiral cyclohexanes and carbasugars. Oxidation of the primary alcohols 6a-b gave the corresponding aldehydes which on treatment with Grignard reagents afforded a mixture of alcohols. The corresponding iodides underwent similar 6-exo-dig cyclisation to give fully functionalised cyclohexanes.