Biomaterial Database

Cycloaddition/Ring opening reaction sequences of N-alkenyl aziridines: influence of the aziridine nitrogen on stereoselectivity. 2008

Matthew R Siebert, and Andrei K Yudin, and Dean J Tantillo

Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, California 95616, USA.

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.

UI	MeSH Term	Description	Entries
D008956	Models, Chemical	Theoretical representations that simulate the behavior or activity of chemical processes or phenomena; includes the use of mathematical equations, computers, and other electronic equipment.	Chemical Models,Chemical Model,Model, Chemical
D009584	Nitrogen	An element with the atomic symbol N, atomic number 7, and atomic weight [14.00643; 14.00728]. Nitrogen exists as a diatomic gas and makes up about 78% of the earth's atmosphere by volume. It is a constituent of proteins and nucleic acids and found in all living cells.
D003500	Cyclization	Changing an open-chain hydrocarbon to a closed ring. (McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed)	Cyclizations
D001388	Aziridines	Saturated azacyclopropane compounds. They include compounds with substitutions on CARBON or NITROGEN atoms.	Ethyleneimines,Azacyclopropanes, Saturated,Dimethyleneimines,Saturated Azacyclopropanes
D013237	Stereoisomerism	The phenomenon whereby compounds whose molecules have the same number and kind of atoms and the same atomic arrangement, but differ in their spatial relationships. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed)	Molecular Stereochemistry,Stereoisomers,Stereochemistry, Molecular,Stereoisomer
D015394	Molecular Structure	The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds.	Structure, Molecular,Molecular Structures,Structures, Molecular