(2+1)-Cycloaddition Reactions Give Further Evidence of the Nitrenium-like Character of 1-Aza-2-azoniaallene Salts.
Cationic 1-aza-2-azoniaallene salts react with structurally constrained alkenes in intramolecular reactions by C-H insertion at the allylic position, or by (2+1)-cycloaddition with the alkene followed by ring opening. The latter reaction gives further evidence of the nitrenium-like character of 1-aza-2-azoniaallene salts. DFT calculations show that alkene addition is intrinsically more favorable, but that predistortion can lead to C-H insertion.
Department of Chemistry, The University of Vermont , Burlington, Vermont 05405, United States.
Nezar
N
Al-Bataineh
Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
K N
0000-0002-8387-5261
KN
Houk
Department of Chemistry, The University of Vermont , Burlington, Vermont 05405, United States.
Matthias
0000-0003-4250-7195
M
Brewer
Department of Chemistry, Zhejiang University , Hangzhou 310027, China.
Xin
X
Hong
D000475:Alkenes / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D066241:Carbon-13 Magnetic Resonance Spectroscopy; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D066244:Proton Magnetic Resonance Spectroscopy; D012492:Salts / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
D000475:Alkenes; D001391:Azo Compounds; D012492:Salts