Rousseau Cyril, Christensen Brian, Petersen Torben Ellebaek, Bols Mikael
Department of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000, Aarhus, Denmark.
Org Biomol Chem. 2004 Dec 7;2(23):3476-82. doi: 10.1039/b410098k. Epub 2004 Nov 1.
Three cyclodextrine derivatives (6A,6D-di-O-(prop-2-one-1,3-dienyl)-alpha-cyclodextrin (1), 6-O-(prop-2-one-1-yl)-alpha-cyclodextrin (2) and 6A,6D-di-O-(prop-2-one-1,3-dienyl)-beta-cyclodextrin (3)) were synthesised and investigated as epoxidation catalysts. The three compounds were synthesised from the corresponding perbenzylated cyclodextrins which were mono- or didebenzylated in the 6-position using Sinaÿ's method. Reaction with NaH and methallyl chloride in the case of 2, or methallyl dichloride in the case of 1 and 3, followed by dihydroxylation, periodate cleavage and protection group removal gave the target compounds. All three compounds catalysed, in the presence of oxone, the epoxidation of a series of alkenes. Epoxidation was compared to the reaction catalysed by simple ketones and inhibition was studied.
合成了三种环糊精衍生物（6A,6D-二-O-（丙-2-烯-1,3-二烯基）-α-环糊精（1）、6-O-（丙-2-烯-1-基）-α-环糊精（2）和6A,6D-二-O-（丙-2-烯-1,3-二烯基）-β-环糊精（3）），并将其作为环氧化催化剂进行了研究。这三种化合物由相应的全苄基化环糊精合成，使用西奈方法在6位进行单苄基化或二苄基化。对于化合物2，与氢化钠和甲基烯丙基氯反应；对于化合物1和3，则与甲基烯丙基二氯反应，随后进行二羟基化、高碘酸盐裂解和保护基团去除，得到目标化合物。在过氧单磺酸钾存在下，所有三种化合物都能催化一系列烯烃的环氧化反应。将该环氧化反应与简单酮催化的反应进行了比较，并研究了抑制作用。
