Cummings Andrew J, Ravalico Francesco, McColgan-Bannon Kegan I S, Eguaogie Olga, Elliott P Alain, Shannon Matthew R, Bermejo Iris A, Dwyer Angus, Maginty Amanda B, Mack James, Vyle Joseph S
a School of Chemistry and Chemical Engineering , Queen's University Belfast , Belfast , UK.
Nucleosides Nucleotides Nucleic Acids. 2015;34(5):361-70. doi: 10.1080/15257770.2014.1001855.
Novel nucleoside analogues containing photoswitchable moieties were prepared using 'click' cycloaddition reactions between 5'-azido-5'-deoxythymidine and mono- or bis-N-propargylamide-substituted azobenzenes. In solution, high to quantitative yields were achieved using 5 mol% Cu(I) in the presence of a stabilizing ligand. 'Click' reactions using the monopropargylamides were also effected in the absence of added cuprous salts by the application of liquid assisted grinding (LAG) in metallic copper reaction vials. Specifically, high speed vibration ball milling (HSVBM) using a 3/32″ (2.38 mm) diameter copper ball (62 mg) at 60 Hz overnight in the presence of ethyl acetate lead to complete consumption of the 5'-azido nucleoside with clean conversion to the corresponding 1,3-triazole.
通过5'-叠氮基-5'-脱氧胸苷与单-N-炔丙基酰胺或双-N-炔丙基酰胺取代的偶氮苯之间的“点击”环加成反应，制备了含有光开关部分的新型核苷类似物。在溶液中，在稳定配体存在下使用5 mol%的Cu(I)可实现高至定量的产率。通过在金属铜反应瓶中应用液体辅助研磨（LAG），在不添加亚铜盐的情况下，单炔丙基酰胺的“点击”反应也能进行。具体而言，在乙酸乙酯存在下，使用直径为3/32英寸（2.38毫米）的铜球（62毫克）在60赫兹下进行高速振动球磨（HSVBM）过夜，可使5'-叠氮基核苷完全消耗，并干净地转化为相应的1,3-三唑。
