Small molecule activation and biomimetic catalysis
Paper
CO2-Mediated Formation of Chiral Carbamates from meso-Epoxides via Polycarbonate Intermediates
Release Time:2019-03-12
Hits:
Indexed by:
Journal Article
First Author:
Liu, Ye
Correspondence Author:
Liu, Y; Lu, XB (reprint author), Dalian Univ Technol, State Key Lab Fine Chem, 2 Linggong Rd, Dalian 116024, Peoples R China.
Co-author:
He, Ke-Ke,Zhang, Wen-Zhen,Li, Wen-Bing,Wang, Meng,Lu, Xiao-Bing,Ren, Wei-Min
Date of Publication:
2016-10-07
Journal:
JOURNAL OF ORGANIC CHEMISTRY
Included Journals:
Scopus、PubMed、EI、SCIE
Document Type:
J
Volume:
81
Issue:
19
Page Number:
8959-8966
ISSN:
0022-3263
Abstract:
Carbon dioxide has attracted broad interest as a renewable C1feedstock for efficient transformation into value-added organic chemicals; nevertheless, far less attention was paid to its stereochemically controlled catalytic fixation/conversion processes. Here, we report a new strategy for the selective synthesis of chiral carbamates from carbon dioxide via polycarbonate intermediates, which are formed by the desymmetric copolymerization of meso-epoxides using enantiopure dinuclear Co(III) catalyst systems with 99% enantioselectivity. Subsequent degradation reaction of the resultant polycarbonates with various primary or secondary amine nucleophiles can afford optically active carbamates, with the complete configuration retention of the two chiral carbon centers. Our accomplishment reported here opens up a new route to prepare a wide range of CO2-based carbamate scaffolds with excellent yields and 99% enantiomeric excess.