文献类型：期刊文献

英文题名：Diastereoselective synthesis of chiral aminophenolate magnesium complexes and their application in the stereoselective polymerization of rac-lactide and rac-β-butyrolactone

作者：Wang, Haobing[1];Guo, Jianshuang;Yang, Yang;Ma, Haiyan[1]

机构：[1]East China Univ Sci & Technol, Shanghai Key Lab Funct Mat Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China; East China Univ Sci & Technol, Lab Organometall Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2016

卷号：45

期号：27

起止页码：10942

外文期刊名：DALTON TRANSACTIONS

收录：;EI(收录号：20162902595703);WOS:【SCI-EXPANDED(收录号:WOS:000379593800011)】；

基金：This work is subsidized by the National Natural Science Foundation of China (NNSFC, 21074032 and 21474028), the Program for New Century Excellent Talents in University (for H. Ma, NCET-06-0413) and the Fundamental Research Funds for the Central Universities (WD1113011). All the financial supports are gratefully acknowledged. H. Ma also thanks the very kind donation of a Braun glove-box by AvH foundation.

语种：英文

外文关键词：X ray analysis - Ligands - Stereoselectivity - Synthesis (chemical) - Magnesium compounds

摘要：A series of magnesium silylamido complexes supported by chiral aminophenolate ligands were synthesized, and their catalytic behaviors toward the ring-opening polymerization of rac-lactide (LA) and rac-beta-butyrolactone (BBL) were explored. The reactions of Mg[N(SiMe3)(2)](2) with chiral tridentate aminophenols L1-10H [L = (S)-{[(1-R-4, 2-pyrrolidinyl)CH2N(R-3)-]}CH2-(6-R-1-4-R-2)-(CH2O)-H-6-] in a 1 : 1 molar ratio in toluene gave the chiral aminophenolate magnesium silylamido complexes L1-10MgN(SiMe3)(2) as enantiopure compounds or as pairs of diastereomers. As determined by X-ray analysis, structures a and b of diastereomer mixtures adopt the configuration of SCSNRNRMg-a and SCSNSNSMg-b, respectively. It was found that most of these magnesium complexes served as highly active initiators for the ring-opening polymerization of rac-LA. Besides, the stereoselectivity of chiral magnesium complexes gradually changed from isoselective-biased (P-m = 0.67) to heteroselective-enriched (P-r = 0.81) via a stepwise adjustment of the substituents of the ligand framework. It was noted that, as the rare reported active magnesium initiator for the ROP of rac-BBL, complexes 3-9 can efficiently initiate the ring-opening polymerization of rac-BBL in a controlled manner, giving moderate syndiotactic (P-s up to 0.73) PHBs.