caa a22 4500 605488533 CHVBK 20210128100455.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00214-014-1606-2 doi (NATIONALLICENCE)springer-10.1007/s00214-014-1606-2 Theoretical investigation on SnCl4-catalyzed tandem dimerization/oxy-2-azonia-Cope rearrangements between β,γ-unsaturated ketones and imines [Elektronische Daten] [Liang Zhang, Jing-Mei Wang, Quan-Rui Wang, Dan-Wei Zhang, Zhan-Ting Li, Zhi-Ming Li] The mechanism of the Lewis acid-catalyzed oxy-2-azonia-Cope rearrangement between β,γ-unsaturated ketones and imines leading to the formation of homoallylic amides and lactams has been theoretically studied using the B3LYP density functional theory methods enhanced with a polarized continuum solvation model. It was predicted that the SnCl4-catalyzed tandem dimerization/oxy-2-azonia-Cope rearrangement mechanism is highly preferred over the uncatalyzed version as well as the plausible tandem dimerization/Prins rearrangement mechanism. A two-step pathway was found for the overall reaction, involving the initial nucleophilic dimerization followed by the [3,3]-sigmatropic rearrangement. The latter phase was considered to be the rate-limiting step. Particularly, the transition states account for the experimentally observed stereoselectivities and Z/E selectivities. The high stereoselectivity and Z/E selectivity for the chiral cyclic substrates can be attributed to the relative conformational stabilities of TSs. Moreover, distortion-interaction analysis has been performed in an attempt to quantify the various contributions to the reaction transition states, and it revealed that interaction energy E int II and distortion energy ∆E d I associated with the formation of the 2COM2 complex are the determining factors to define the Z/E selectivities for nine- and ten-membered ring pathway, respectively. Investigation on the ethyleneimine-involved reaction predicts a relatively very low barrier in the pathway; thus, the sequence might be a useful strategy for synthesis of macrolactams. Springer-Verlag Berlin Heidelberg, 2015 Oxy-2-azonia-Cope rearrangement nationallicence Prins rearrangement nationallicence Density functional theory nationallicence β,γ-Unsaturated ketone nationallicence Distortion-interaction analysis nationallicence Zhang Liang Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut Wang Jing-Mei Research Centre for Analysis & Measurement, Fudan University, 200433, Shanghai, China aut Wang Quan-Rui Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut Zhang Dan-Wei Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut Li Zhan-Ting Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut Li Zhi-Ming Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-14 1432-881X 134:2<1 2015 134 214 https://doi.org/10.1007/s00214-014-1606-2 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-014-1606-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zhang Liang Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut NATIONALLICENCE 700 1- Wang Jing-Mei Research Centre for Analysis & Measurement, Fudan University, 200433, Shanghai, China aut NATIONALLICENCE 700 1- Wang Quan-Rui Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut NATIONALLICENCE 700 1- Zhang Dan-Wei Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut NATIONALLICENCE 700 1- Li Zhan-Ting Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut NATIONALLICENCE 700 1- Li Zhi-Ming Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-14 1432-881X 134:2<1 2015 134 214