Li Hong, Pang Zi-Bo, Jiao Zhi-Feng, Lin Fei
Key Laboratory of Functional Polymer Materials of Education Ministry, Institute of Polymer Chemistry, Nankai University, Tianjin 300071, China.
J Comb Chem. 2010 Mar 8;12(2):255-9. doi: 10.1021/cc900162w.
A novel microgel-supported acylating reagent (MGAR) was prepared by combining ring-opening metathesis polymerization (ROMP) and Activators Re-Generated by Electron Transfer for Atom Transfer Radical Polymerization (ARGET ATRP): (1) synthesis of an ATRP macroinitiator 3 by living ROMP of oxanorbornene-based activated ester 1, derived from N-hydroxysuccinimide, using the Grubbs initiator RuCl(2)(PCy(3))(2)(=CHPh) and (Z)-but-2-ene-1,4-diyl bis(2-bromopropanoate) (BDBP) as a terminating agent; (2) synthesis of MGAR 4 by ARGET ATRP of styrene (S) and divinylbenzene (DVB) using the prepared macroinitiator 3, a CuCl(2)/Me(6)TREN (tris[2-(dimethylamino)ethyl]amine) catalyst system, a Sn(Oct)(2) [tin(II)2-ethylhexanoate] reducing agent. The synthesized microgels 4 exhibit excellent acyl (acetyl, benzoyl, phenylsulfonyl) transfer properties for primary and secondary amines (n-BuNH(2), Et(2)NH, morpholine, etc.) under mild conditions (25 degrees C, 13.5-14 h) affording N-acylamines with high yield (95.6-100%) and purity (94.1-96.0%).
通过开环易位聚合（ROMP）和电子转移再生催化剂原子转移自由基聚合（ARGET ATRP）相结合，制备了一种新型微凝胶负载的酰化试剂（MGAR）：（1）以N-羟基琥珀酰亚胺衍生的氧杂降冰片烯基活性酯1为原料，使用格拉布催化剂RuCl(2)(PCy(3))(2)(=CHPh)和(Z)-丁-2-烯-1,4-二基双(2-溴丙酸酯)(BDBP)作为封端剂，通过活性ROMP合成ATRP大分子引发剂3；（2）使用制备的大分子引发剂3、CuCl(2)/Me(6)TREN（三[2-(二甲基氨基)乙基]胺）催化剂体系、Sn(Oct)(2) [二(2-乙基己酸)锡(II)]还原剂，通过苯乙烯（S）和二乙烯基苯（DVB）的ARGET ATRP合成MGAR 4。合成的微凝胶4在温和条件下（25℃，13.5 - 14小时）对伯胺和仲胺（正丁胺、二乙胺、吗啉等）表现出优异的酰基（乙酰基、苯甲酰基、苯磺酰基）转移性能，能够高产率（95.6 - 100%）和高纯度（94.1 - 96.0%）地得到N-酰基胺。
