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Towards an Understanding of the Polar Diels–Alder Reactions of Nitrosoalkenes with Enamines: A Theoretical Study

✍ Scribed by Luis R. Domingo; M. Teresa Picher; Pau Arroyo

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
212 KB
Volume
2006
Category
Article
ISSN
1434-193X

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✦ Synopsis

Abstract

The polar Diels–Alder reactions of nitrosoalkenes with enamines have been studied using DFT methods at the B3LYP/6‐31G* level of theory. These Diels–Alder reactions are characterized by a nucleophilic attack of the enamine at the conjugated position of the nitrosoalkene with concomitant ring‐closure. The reactions present a total regioselectivity and a large endo selectivity. The analysis, based on the global electrophilicity of the reagents in the ground state, the natural bond orbital (NBO), and the topological analysis of the electron localization function (ELF) in the endo transition state (TS) and “halfway” along the IRC between the TS and cycloadduct, correctly explain the polar nature of these cycloaddition reactions. The large electrophilic character of nitrosoethylenes together with the large nucleophilic character of enamines are responsible for the large acceleration found in these polar Diels–Alder reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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