Portal de Periódicos da CAPES

A DFT Study on Mechanisms and Origin of Selectivity of Phosphine-Catalyzed Vicinal Acylcyanation of Alkynoates

2017; Wiley; Volume: 2; Issue: 19 Linguagem: Inglês

10.1002/slct.201700996

2365-6549

Wei Wang, Yang Wang, Linjie Zheng, Yan Qiao, Donghui Wei,

Synthesis and Catalytic Reactions

ChemistrySelectVolume 2, Issue 19 p. 5266-5273 Full Paper A DFT Study on Mechanisms and Origin of Selectivity of Phosphine-Catalyzed Vicinal Acylcyanation of Alkynoates Wei Wang, Wei Wang orcid.org/0000-0003-2820-282X The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorDr. Yang Wang, Dr. Yang Wang The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorLinjie Zheng, Linjie Zheng The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorDr. Yan Qiao, Corresponding Author Dr. Yan Qiao yanqiao@zzu.edu.cn Department of Pathophysiology, School of Basic Medical Sciences, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorProf. Donghui Wei, Corresponding Author Prof. Donghui Wei donghuiwei@zzu.edu.cn The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this author Wei Wang, Wei Wang orcid.org/0000-0003-2820-282X The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorDr. Yang Wang, Dr. Yang Wang The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorLinjie Zheng, Linjie Zheng The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorDr. Yan Qiao, Corresponding Author Dr. Yan Qiao yanqiao@zzu.edu.cn Department of Pathophysiology, School of Basic Medical Sciences, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this authorProf. Donghui Wei, Corresponding Author Prof. Donghui Wei donghuiwei@zzu.edu.cn The College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, Henan Province, 450001 P. R. ChinaSearch for more papers by this author First published: 04 July 2017 https://doi.org/10.1002/slct.201700996Citations: 18Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract The possible mechanisms and origin of stereoselectivity on phosphine-catalyzed vicinal acylcyanation of alkynoates have been investigated for the first time by density functional theory (DFT) method. The natural bond orbital (NBO) population, global reactivity index (GRI), and non-covalent interaction (NCI) analyses indicate that phosphine plays an important role for promoting reaction and improving the stereoselectivity. This work would provide valuable insights into rational design of phosphine-catalyzed vicinal acylcyanation of alkynoates with high anti/syn-selectivity. Abstract The mechanisms of phosphine-catalyzed vicinal acylcyanation of alkynoates have been firstly investigated by density functional theory. Both PPhMe2- and PBu3-catalyzed reactions were enumerated and studied in detail. For each reaction, three possible pathways, including the direct pathway that leads to syn-selective product and two phosphine-catalyzed reaction pathways that lead to anti- and syn-selective products respectively, were considered in this work. The calculated results indicate that the most energetically favorable pathway contains five reaction steps: the nucleophilic attack on alkynoate by phosphine, the acylation by acylcyanide, the dissociation of CN group from acylcyanide, the addition of CN group to olefin carbon of alkynoate part, and the dissociation of phosphine and product. The last two steps are the key for the anti/syn-selectivity of reactions, and our computational results can reasonably explain the experimental observations. In addition, non-covalent interaction analysis was performed for exploring the origin of the anti/syn-selectivity. Moreover, the natural bond orbital (NBO) population and global reactivity index (GRI) analyses were also carried out to disclose the role of the phosphine catalyst in this kind of reaction. This work should be helpful for chemists to understand the detailed mechanisms and predict anti/syn-selectivity of this kind of vicinal acylcyanation. Conflict of interest The authors declare no conflict of interest. Citing Literature Supporting Information As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Filename Description slct201700996-sup-0001-misc_information.pdf570.1 KB Supplementary Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. Volume2, Issue19July 3, 2017Pages 5266-5273 RelatedInformation