Density functional theory studies on the mechanisms of regioselective allylic and cis-vinylic deprotonation of allyl amides and allylamines.
A density functional theory (B3LYP/6-31+G) study was undertaken in an effort to learn more about the mechanisms controlling the regioselective deprotonations of the synthetically versatile N-lithio-N-(tert-butyl)allylamide 1 and N-lithio-N-(trimethylsilyl)allylamine 2 compounds. The calculations suggest that deprotonation of 1 occurs exclusively at the allylic position. This agrees with experimental results. The calculations also suggest that deprotonation of allylamine 2 exclusively at the cis-vinylic position is due to kinetic control.
Haeffner
Fredrik
F
Department of Chemistry, Brown University, Providence, RI 02912, USA. fredrick_haeffner@brown.edu
Jacobson
Madeleine A
MA
Keresztes
Ivan
I
Williard
Paul G
PG
D000498:Allyl Compounds / Q000737:chemistry; D000499:Allylamine / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry; D011522:Protons; D013379:Substrate Specificity; D014753:Vinyl Compounds / Q000737:chemistry*
D000498:Allyl Compounds; D000577:Amides; D009942:Organometallic Compounds; D011522:Protons; D014753:Vinyl Compounds; D000499:Allylamine; D008094:Lithium