Synthesis and Application of a Microgel-Supported Acylating Reagent by Coupled Ring-Opening Metathesis Polymerization and Activators Re-Generated by Electron Transfer for Atom Transfer Radical Polymerization

• Published in: Journal of combinatorial chemistry Vol. 12; no. 2; pp. 255 - 259
• Main Authors: Li, Hong, Pang, Zi-Bo, Jiao, Zhi-Feng, Lin, Fei
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 08.03.2010; Amer Chemical Soc
• Subjects: Acylation; Chemistry; Chemistry, Applied; Chemistry, Medicinal; Chemistry, Multidisciplinary; Cyclization; Indicators and Reagents - chemical synthesis; Indicators and Reagents - chemistry; Life Sciences & Biomedicine; Pharmacology & Pharmacy; Physical Sciences; Polymers - chemistry; Science & Technology; ORGANIC-SYNTHESIS; SOLUBLE POLYMERS; PURIFICATION; LIBRARY; BENZYLATION; CHEMISTRY; HIGH-LOAD; FACILE; PARALLEL SYNTHESIS; CATALYSTS
• ISSN: 1520-4766; 1520-4774
• 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 RuCl2(PCy3)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 CuCl2/Me6TREN (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-BuNH2, Et2NH, morpholine, etc.) under mild conditions (25 °C, 13.5−14 h) affording N-acylamines with high yield (95.6−100%) and purity (94.1−96.0%).