Alternating Sequence Controlled Copolymer Synthesis of α-Hydroxy Acids via Syndioselective Ring-Opening Polymerization of O-Carboxyanhydrides Using Zirconium/Hafnium Alkoxide Initiators

Yangyang Sun; Zhaowei Jia; Changjuan Chen; Yong Cong; Xiaoyang Mao; Jincai Wu

doi:10.1021/jacs.7b04712

Alternating Sequence Controlled Copolymer Synthesis of α-Hydroxy Acids via Syndioselective Ring-Opening Polymerization of O-Carboxyanhydrides Using Zirconium/Hafnium Alkoxide Initiators

J Am Chem Soc. 2017 Aug 9;139(31):10723-10732. doi: 10.1021/jacs.7b04712. Epub 2017 Jul 28.

Authors

Yangyang Sun¹, Zhaowei Jia¹, Changjuan Chen^{1

2}, Yong Cong¹, Xiaoyang Mao¹, Jincai Wu¹

Affiliations

¹ State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University , Lanzhou 730000, People's Republic of China.
² College of Chemistry and Pharmaceutical Engineering, Huanghuai University , Zhumadian 463000, People's Republic of China.

PMID: 28715211
DOI: 10.1021/jacs.7b04712

Abstract

The ring-opening polymerization (ROP) of O-carboxyanhydrides (OCAs) can give diverse poly(α-hydroxy acid)s (PAHAs) with different functional groups because of easy modification of the side group of OCAs, which can extend applications of PAHAs widely. The stereoselective polymerization of O-carboxyanhydrides and further sequence controlled alternating copolymerization of OCAs were still big challenges until now for lack of suitable catalysts/initiators. In this work, a highly syndioselective ROP of OCAs system as the first stereoselective example in this area is reported using zirconium/hafnium alkoxides as initiators with the highest P_r value up to 0.95. Furthermore, these initiators were successfully applied in the precisely alternating sequence controlled copolymerization of PheOCA and Tyr(Bn)OCA, and alternating copolymerization of LacOCA and PheOCA was also achieved.

Publication types

Research Support, Non-U.S. Gov't