title: CO2-Mediated Formation of Chiral Carbamates from meso-Epoxides via Polycarbonate Intermediates.
abstract: Carbon dioxide has attracted broad interest as a renewable C1 feedstock 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.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Ye
authors.initials: Y
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Wei-Min
authors.initials: WM
authors.lastname: Ren
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Ke-Ke
authors.initials: KK
authors.lastname: He
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Wen-Zhen
authors.initials: WZ
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Wen-Bing
authors.initials: WB
authors.lastname: Li
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Meng
authors.initials: M
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology , 2 Linggong Road, Dalian 116024, China.
authors.forename: Xiao-Bing
authors.initials: XB
authors.lastname: Lu