Theoretical insight into the mechanism of gold(I)-catalyzed rearrangement of 2-propargyl 2H-azirines to pyridines

The Journal of Organic Chemistry
Lu JinXiang Zhao

Abstract

The title reaction is investigated in detail theoretically using density functional theory. After 5-endo-dig cyclization by nucleophilic attack, five possible pathways are taken into account in this work: direct ring expansion followed or accompanied by proton-transfer (paths A and B, respectively), 1,3-cationic migration (path C), proton-transfer before ring expansion (path D), and processing via a gold-nitrene (path E). Results indicate that the reaction would undergo the favored sequential pathway (path A) rather than other pathways. Moreover, the concerted mechanism (path B), which is designed to account for the selectivity of product in the experiment, would be unlikely in the reaction. The selectivity of product could be explained by the hindrance of ligand (t-BuXPhos) and the stability of the carbocation. Moreover, the binding energy of product complexes could account for the observed reaction rate.

References

Jan 28, 2006·The Journal of Chemical Physics·Stefan Grimme
Mar 28, 2007·Organic Letters·Franklin A Davis, Jianghe Deng
Dec 5, 2008·Organic Letters·Christophe GourlaouenFeliu Maseras
Jul 31, 2010·Angewandte Chemie·Changkun LiJianbo Wang
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Jun 25, 2013·The Journal of Organic Chemistry·Ana Lúcia CardosoTeresa M V D Pinho e Melo
Oct 1, 2013·The Journal of Organic Chemistry·Cláudio M NunesRui Fausto
Oct 31, 2013·Accounts of Chemical Research·Di-Han ZhangMin Shi
Nov 2, 2013·Accounts of Chemical Research·Carla Obradors, Antonio M Echavarren
Nov 16, 2013·Accounts of Chemical Research·Yi-Ming WangF Dean Toste
Dec 25, 2013·The Journal of Organic Chemistry·Xiaoming ZhangAnna D Gudmundsdottir
Jan 17, 2014·Accounts of Chemical Research·Liming Zhang
Jan 17, 2014·Accounts of Chemical Research·Benito Alcaide, Pedro Almendros
Feb 13, 2014·Accounts of Chemical Research·Hyun-Suk Yeom, Seunghoon Shin
Feb 13, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Caihong WuBo Yan
Feb 19, 2014·Accounts of Chemical Research·A Stephen K Hashmi
Feb 26, 2014·Accounts of Chemical Research·Louis Fensterbank, Max Malacria
May 24, 2014·Chemical Society Reviews·Jin XieChengjian Zhu
May 30, 2014·Chemical Reviews·Chung-Yang Dennis Huang, Abigail G Doyle
Dec 19, 2014·Chemical Society Reviews·Deyun Qian, Junliang Zhang
Mar 11, 2014·Journal of Chemical Theory and Computation·Gianluca CiancaleoniLeonardo Belpassi

❮ Previous
Next ❯

Related Concepts

Related Feeds

Cell Migration

Cell migration is involved in a variety of physiological and pathological processes such as embryonic development, cancer metastasis, blood vessel formation and remoulding, tissue regeneration, immune surveillance and inflammation. Here is the latest research.