Cycloaddition/Ring Opening Reaction Sequences of N -Alkenyl Aziridines: Influence of the Aziridine Nitrogen on Stereoselectivity
Abstract
The cycloaddition of (Z)-7-(prop-1-enyl)-7-azabicyclo[4.1.0]heptane with dimethyl acetylene dicarboxylate (DMAD) was reported previously to proceed with complete stereoselectivity. Quantum chemical calculations (B3LYP) were used to evaluate the mechanism of the cyclization process, and it was discovered that a stepwise pathway is preferred. The subsequent electrocyclic ring opening reaction of the cyclobutene was also studied, and it was found that ring opening to the "methyl-in" dienamine is preferred to the "methyl-out" product by some 4-5 kcal/mol.
Department(s)
Chemistry and Biochemistry
Document Type
Article
DOI
https://doi.org/10.1021/ol702623d
Keywords
aziridines, cyclization, stereoselectivity, chemical structure, nitrogen
Publication Date
2008
Recommended Citation
Siebert, Matthew R., Andrei K. Yudin, and Dean J. Tantillo. "Cycloaddition/Ring opening reaction sequences of n-alkenyl aziridines: influence of the aziridine nitrogen on stereoselectivity." Organic letters 10, no. 1 (2008): 57-60.
Journal Title
Organic letters
