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论文类型：期刊论文

发表时间：2016-10-07

发表刊物：JOURNAL OF ORGANIC CHEMISTRY

收录刊物：SCIE、EI、PubMed、Scopus

卷号：81

期号：19

页面范围：8959-8966

ISSN号：0022-3263

摘要：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.