Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kyoto, Japan.
Carbohydr Res. 2013 Dec 15;382:25-9. doi: 10.1016/j.carres.2013.09.010. Epub 2013 Oct 8.
The tandem Staudinger/aza-Wittig reaction of the 6-azido-6-deoxycellulose derivative (2) with triphenylphosphine and carbon disulfide afforded the corresponding 6-isothiocyanato-6-deoxycellulose derivative (3) in 47.3% yield. Compound 3 was further reacted with 4'-aminobenzo-15-crown ether to afford the crown ether-containing 6-N-thioureido-6-deoxycellulose derivative (4) in 70.0% yield. Compound 4 was also obtained in 28.7% yield from the one-pot reaction (tandem Staudinger/aza-Wittig reaction/thiocarbamoylation) of compound 2. The tandem Staudinger/aza-Wittig reaction is a useful alternative to the Huisgen reaction for the synthesis of functional cellulose derivatives from 6-azido-6-deoxycellulose derivatives.
6-叠氮基-6-脱氧纤维素衍生物(2)与三苯基膦和二硫化碳的串联 Staudinger/aza-Wittig 反应以 47.3%的收率得到相应的 6-异硫氰酸酯-6-脱氧纤维素衍生物(3)。化合物 3 进一步与 4'-氨基苯并-15-冠醚反应,以 70.0%的收率得到含冠醚的 6-N-硫代尿基-6-脱氧纤维素衍生物(4)。化合物 4 也可以通过化合物 2 的一锅反应(串联 Staudinger/aza-Wittig 反应/硫代氨基甲酰化)以 28.7%的收率得到。串联 Staudinger/aza-Wittig 反应是一种从 6-叠氮基-6-脱氧纤维素衍生物合成功能性纤维素衍生物的有用替代方法,而不是 Huisgen 反应。