Abstract: A new type of adamantane-supported hypervalent iodine reagents 1a-1c were prepared by acylation and oxidation with 1,3,5,7-tetraaminoadamantane and 4-iodobenzoylchloride. The acylation reaction was first performed at 0 ℃ for 4 h, and then at room temperature for 2 h. The molar ratio of substrates is n(1,3,5,7-tetramamantadine)∶n(4-iodiphenyl chloride)∶n(triethylamine)=1∶4.4∶5.2. CH₂Cl₂/acetic acid (volume ratio 1∶1) was used as the solvent and m-chloroperoxybenzoic acid(m-CPBA) was used as the oxidant for the oxidation reaction which takes 12 h at room temperature, and the feed ratio of intermediate 2 to m-CPBA is 1∶12. The total yields of compounds 1a, 1b and 1c are 86.4%, 85.4% and 85.3%, respectively. Various alcohols were oxidized into corresponding aldehydes or ketones by using compounds 1a-1c as the oxidant and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as the catalyst. The yield of aldehydes or ketones are 87%~100%. The load iodobenzenes 2a-2c can be easily separated and recovered, the average recovery is 98%, and it can be reoxidized into compounds 1a-1c with high yield for recycling.

Key words: Adamantane-supported hypervalent iodine reagent, 1,3,5,7-Tetraaminoadamantane, 4-Iodobenzoylchloride, Alcohol oxidation