Theoretical investigation on SnCl4-catalyzed tandem dimerization/oxy-2-azonia-Cope rearrangements between β,γ-unsaturated ketones and imines
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| 024 | 7 | 0 | |a 10.1007/s00214-014-1606-2 |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00214-014-1606-2 | ||
| 245 | 0 | 0 | |a Theoretical investigation on SnCl4-catalyzed tandem dimerization/oxy-2-azonia-Cope rearrangements between β,γ-unsaturated ketones and imines |h [Elektronische Daten] |c [Liang Zhang, Jing-Mei Wang, Quan-Rui Wang, Dan-Wei Zhang, Zhan-Ting Li, Zhi-Ming Li] |
| 520 | 3 | |a 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. | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Oxy-2-azonia-Cope rearrangement |2 nationallicence | |
| 690 | 7 | |a Prins rearrangement |2 nationallicence | |
| 690 | 7 | |a Density functional theory |2 nationallicence | |
| 690 | 7 | |a β,γ-Unsaturated ketone |2 nationallicence | |
| 690 | 7 | |a Distortion-interaction analysis |2 nationallicence | |
| 700 | 1 | |a Zhang |D Liang |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | |
| 700 | 1 | |a Wang |D Jing-Mei |u Research Centre for Analysis & Measurement, Fudan University, 200433, Shanghai, China |4 aut | |
| 700 | 1 | |a Wang |D Quan-Rui |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | |
| 700 | 1 | |a Zhang |D Dan-Wei |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | |
| 700 | 1 | |a Li |D Zhan-Ting |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | |
| 700 | 1 | |a Li |D Zhi-Ming |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | |
| 773 | 0 | |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/2(2015-02-01), 1-14 |x 1432-881X |q 134:2<1 |1 2015 |2 134 |o 214 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00214-014-1606-2 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00214-014-1606-2 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Zhang |D Liang |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Wang |D Jing-Mei |u Research Centre for Analysis & Measurement, Fudan University, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Wang |D Quan-Rui |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Zhang |D Dan-Wei |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Li |D Zhan-Ting |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Li |D Zhi-Ming |u Department of Chemistry, Fudan University, 220 Handan Road, 200433, Shanghai, China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/2(2015-02-01), 1-14 |x 1432-881X |q 134:2<1 |1 2015 |2 134 |o 214 | ||