Format

Send to

Choose Destination
Nat Commun. 2019 Sep 11;10(1):4122. doi: 10.1038/s41467-019-12102-y.

Reaction selectivity of homochiral versus heterochiral intermolecular reactions of prochiral terminal alkynes on surfaces.

Author information

1
National Synchrotron Radiation Laboratory, Department of Chemical Physics and Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, 230029, Hefei, People's Republic of China.
2
Hefei National Laboratory of Physical Sciences at the Microscale, University of Science and Technology of China, 230026, Hefei, People's Republic of China.
3
Department of Materials Science and Engineering, CAS Key Laboratory of Materials for Energy Conversion, and CAS Center for Excellence in Nanoscience, University of Science and Technology of China, 230026, Hefei, People's Republic of China.
4
Hefei National Laboratory of Physical Sciences at the Microscale, University of Science and Technology of China, 230026, Hefei, People's Republic of China. adzhao@ustc.edu.cn.
5
Hefei National Laboratory of Physical Sciences at the Microscale, University of Science and Technology of China, 230026, Hefei, People's Republic of China. xjwu@ustc.edu.cn.
6
Department of Materials Science and Engineering, CAS Key Laboratory of Materials for Energy Conversion, and CAS Center for Excellence in Nanoscience, University of Science and Technology of China, 230026, Hefei, People's Republic of China. xjwu@ustc.edu.cn.
7
Department of Chemistry, Indiana University, Bloomington, IN, 47405, USA.
8
National Synchrotron Radiation Laboratory, Department of Chemical Physics and Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, 230029, Hefei, People's Republic of China. jfzhu@ustc.edu.cn.
9
Dalian National Laboratory for Clean Energy, 116023, Dalian, People's Republic of China. jfzhu@ustc.edu.cn.

Abstract

Controlling selectivity between homochiral and heterochiral reaction pathways on surfaces remains a great challenge. Here, competing reactions of a prochiral alkyne on Ag(111): two-dimensional (2D) homochiral Glaser coupling and heterochiral cross-coupling with a Bergman cyclization step have been examined. We demonstrate control strategies in steering the reactions between the homochiral and heterochiral pathways by tuning the precursor substituents and the kinetic parameters, as confirmed by high-resolution scanning probe microscopy (SPM). Control experiments and density functional theory (DFT) calculations reveal that the template effect of organometallic chains obtained under specific kinetic conditions enhances Glaser coupling between homochiral molecules. In contrast, for the reaction of free monomers, the kinetically favorable reaction pathway is the cross-coupling between two heterochiral molecules (one of them involving cyclization). This work demonstrates the application of kinetic control to steer chiral organic coupling pathways at surfaces.

Supplemental Content

Full text links

Icon for Nature Publishing Group Icon for PubMed Central
Loading ...
Support Center