Ahmadibeni Yousef, Parang Keykavous
Department of Biomedical and Pharmaceutical Sciences, College of Pharmacy, The University of Rhode Island, Kingston, RI 02881, USA.
J Org Chem. 2005 Feb 4;70(3):1100-3. doi: 10.1021/jo048113e.
Two classes of aminomethyl polystyrene resin-bound linkers of p-acetoxybenzyl alcohol were subjected to reactions with 2-cyanoethyl N,N-diisopropylchlorophosphoramidite to produce the corresponding polymer-bound phosphitylating reagents. These were reacted with a number of unprotected nucleosides and carbohydrates in the presence of 1H-tetrazole. Oxidation with tert-butyl hydroperoxide followed by removal of the cyanoethoxy group with 1,8-diazabicyclo[5.4.0]undec-7-ene afforded the corresponding polymer-bound phosphate diesters. Acidic cleavage of the p-acetoxybenzyl alcohol linker yielded monophosphorylated products with high regioselectivity and trapped linkers on the resins that can be reused.
将两类对乙酰氧基苄醇的氨甲基聚苯乙烯树脂连接体与2-氰基乙基-N,N-二异丙基氯代亚磷酰胺进行反应，以制备相应的聚合物负载的亚磷酸化试剂。在1H-四唑存在下，将这些试剂与多种未保护的核苷和碳水化合物反应。用叔丁基过氧化氢氧化，然后用1,8-二氮杂双环[5.4.0]十一碳-7-烯除去氰乙氧基，得到相应的聚合物负载的磷酸二酯。对乙酰氧基苄醇连接体的酸解产生具有高区域选择性的单磷酸化产物，并将连接体捕获在可重复使用的树脂上。
