title: Copper nanocrystal plane effect on stereoselectivity of catalytic deoxygenation of aromatic epoxides.
abstract: Previous studies have shown that crystal planes of heterogeneous catalysts could display enhanced activity, such that higher turnover or chemoselectivity could be achieved. Here we report an example where the reaction stereoselectivity was significantly affected by the catalyst crystal planes. In copper-catalyzed deoxygenation reaction of aromatic epoxides, copper cubes, wires, and plates gave the olefin products with different cis/trans selectivities, whereas homogeneous copper catalysts showed poor selectivity. Scanning tunneling microscope and density functional theory studies revealed that the different adsorption mode and higher adsorption strength of epoxide oxygen on Cu{100} plane were responsible for the observed variation of selectivity. The copper-catalyzed deoxygenation reaction provided new practical access to cis-olefins from readily available aromatic epoxides. Our work also indicated that nanocrystal catalysts may provide useful stereochemical control in organic reactions.
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.|‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Bin
authors.initials: B
authors.lastname: Xiao
authors.affiliation: ‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Niu
authors.affiliation: ‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Yang-Gang
authors.initials: YG
authors.lastname: Wang
authors.affiliation: ‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Jia
authors.affiliation: ∥College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
authors.forename: Jian
authors.initials: J
authors.lastname: Shang
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.
authors.forename: Lan
authors.initials: L
authors.lastname: Zhang
authors.affiliation: ‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Dingsheng
authors.initials: D
authors.lastname: Wang
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.
authors.forename: Yao
authors.initials: Y
authors.lastname: Fu
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.
authors.forename: Jie
authors.initials: J
authors.lastname: Zeng
authors.affiliation: §Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.|⊥Tsinghua-Peking Center for Life Sciences, Tsinghua University, Beijing 100084, China.
authors.forename: Wei
authors.initials: W
authors.lastname: He
authors.affiliation: ∥College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
authors.forename: Kai
authors.initials: K
authors.lastname: Wu
authors.affiliation: ‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Li
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.
authors.forename: Jinlong
authors.initials: J
authors.lastname: Yang
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.|‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.|⊥Tsinghua-Peking Center for Life Sciences, Tsinghua University, Beijing 100084, China.
authors.forename: Lei
authors.initials: L
authors.lastname: Liu
authors.affiliation: †Center of Advanced Nanocatalysis (CAN), University of Science and Technology of China, Hefei 230026, China.|‡Department of Chemistry, Tsinghua University, Beijing 100084, China.|§Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China.
authors.forename: Yadong
authors.initials: Y
authors.lastname: Li