Thermodynamic and kinetic factors in the aza-Cope rearrangement of a series of iminium cations

Autor:	M.C. Milletti, Harriet A. Lindsay, Powen Hsueh, Mark Lukowski, Kathryn Jacobs
Rok vydání:	2009
Předmět:	chemistry.chemical_classification Double bond Chemistry Stereochemistry Organic Chemistry Iminium Biochemistry Transition state Chemical bond Computational chemistry Drug Discovery Aza-Cope rearrangement Chemical stability Stereoselectivity Cope rearrangement
Zdroj:	Tetrahedron. 65:10311-10316
ISSN:	0040-4020
DOI:	10.1016/j.tet.2009.10.010
Popis:	The effects of C–C bond conformation, double bond geometry, and relative stereochemistry on the kinetic and thermodynamic stability of 30 iminium cations as they undergo an aza-Cope rearrangement have been examined via density functional calculations for the purposes of predicting stereoselectivity in the reaction sequence. DFT predicted transition states were consistent with experimentally observed stereoselectivities. The calculations were then extended to the rearrangements of other iminium cations with varying substitution patterns to identify trends in rearrangement pathways. These trends should provide insight into controlling stereoselectivity in this reaction sequence.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::53fbe76b456a8bcd34e515cbf50e95f7 https://doi.org/10.1016/j.tet.2009.10.010 Zobrazit plný text záznamu Full Text from ScienceDirect