Abstract
We report how mechanistically inspired metal additive choices result in acceleration of the copper catalyzed vinyl aziridine ring expansion reaction. Most importantly, we demonstrate how the use of in situ reducing agents significantly accelerates the reaction, suggesting a copper(i) active species. These acceleration results were confirmed using Cu(hfacac)(cod) as catalyst. NMR kinetic studies revealed the relative importance of olefin and sulfonamide electronics on the reaction rate and established the order of both catalyst and substrate, which together favored a new copper(i) insertion mechanism.
Original language | English (US) |
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Pages (from-to) | 3321-3325 |
Number of pages | 5 |
Journal | Chemical Science |
Volume | 3 |
Issue number | 11 |
DOIs | |
State | Published - Nov 2012 |
Externally published | Yes |
ASJC Scopus subject areas
- General Chemistry
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CCDC 886193: Experimental Crystal Structure Determination
MacK, D. J. (Contributor) & Njardarson, J. T. (Creator), Cambridge Crystallographic Data Centre, 2013
DOI: 10.5517/ccyr4wp, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccyr4wp&sid=DataCite
Dataset
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CCDC 886194: Experimental Crystal Structure Determination
MacK, D. J. (Contributor) & Njardarson, J. T. (Creator), Cambridge Crystallographic Data Centre, 2013
DOI: 10.5517/ccyr4xq, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccyr4xq&sid=DataCite
Dataset
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CCDC 886192: Experimental Crystal Structure Determination
MacK, D. J. (Contributor) & Njardarson, J. T. (Creator), Cambridge Crystallographic Data Centre, 2013
DOI: 10.5517/ccyr4vn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccyr4vn&sid=DataCite
Dataset