金刚烷负载高价碘试剂的合成及氧化反应活性

以1,3,5,7-四氨基金刚烷与4-碘苯基酰氯为原料,经酰化、氧化反应,制备了新型金刚烷负载的高价碘试剂(1a-1c)。 酰化反应以CH₂Cl₂为溶剂,首先,0 ℃,反应4 h,然后室温反应2 h,投料比n(1,3,5,7-四氨基金刚烷)∶n(4-碘苯基酰氯)∶n(三乙胺)=1∶4.4∶5.2。 氧化反应以CH₂Cl₂/醋酸(体积比1∶1)为溶剂,间氯过氧苯甲酸(m-CPBA)为氧化剂,室温反应12 h,投料比n(2)∶n(m-CPBA)=1∶12。 化合物1a,1b和1c的总收率分别为86.4%、85.4%和85.3%。 以化合物1a-1c为氧化剂,在四甲基哌啶氮氧化物(TEMPO)催化下各类醇被氧化成相应的醛或酮,产物收率87%~100%。 负载碘苯2a-2c可以被方便地分离和回收,平均回收率98%,可再经氧化,高收率转化成化合物1a-1c,循环利用。

Synthesis and Oxidation Activity of Adamantane Supported Hypervalent Iodine Reagent

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.