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

• Published in: Nature communications Vol. 10; no. 1; pp. 4122 - 9
• Main Authors: Wang, Tao, Lv, Haifeng, Huang, Jianmin, Shan, Huan, Feng, Lin, Mao, Yahui, Wang, Jinyi, Zhang, Wenzhao, Han, Dong, Xu, Qian, Du, Pingwu, Zhao, Aidi, Wu, Xiaojun, Tait, Steven L., Zhu, Junfa
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 11-09-2019; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/146; 147/136; 147/138; 147/3; 639/638/440/950; 639/638/542/968; 639/638/563/979; Alkynes; Chemistry; Coupling (molecular); Cross coupling; Density functional theory; Humanities and Social Sciences; Laboratories; Microscopy; Molecular structure; Monomers; multidisciplinary; Radiation; Scanning probe microscopy; Science; Science (multidisciplinary); Selectivity; Silver; Steering
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-019-12102-y

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.
Controlling selectivity between homochiral and heterochiral reaction pathways on surfaces is intriguing but challenging. Here, the authors demonstrate strategies in steering the reactions of prochiral terminal alkynes between the homochiral and heterochiral pathways by tuning the precursor substituents and the kinetic parameters.