Lewis acid-promoted Kharasch-Curran additions: a competition kinetics study of bromine atom transfer addition of N-alpha-bromoacetyl-oxazolidinone to 1-hexene.
Lewis acids can efficiently promote free radical atom transfer reactions of an oxazolidinone imide substrate, 1, derived from alpha-bromo acetic acid. Thus, 1 undergoes a radical chain addition to 1-hexene giving the atom transfer addition compound, 6, in the presence of scandium or ytterbium triflate in 1,2-dichloroethane or a cosolvent mixture of 1/9 THF/dichloromethane. In 1,2-dichloroethane the solution is heterogeneous, while the cosolvent mixture gives a homogeneous solution, even at temperatures of -78 degrees C. Competition experiments were carried out in both solvent systems with added carbon tetrachloride to study how Lewis acid affected the product distribution. In the presence of carbon tetrachloride, chloride 7 is formed in addition to 6 and the ratio of these two products depends on the amount of Lewis acid present. In the presence of ytterbium triflate, in the cosolvent system, the reaction rate of bromine atom transfer was enhanced up to 400-fold compared to the reaction without added Lewis acid. Significant rate enhancements were also obtained in the solvent 1,2-dichloroethane, although the analysis of the system is complicated by the heterogeneous nature of the medium. Computation of C-Br bond dissociation energies (BDE) of the complexed and uncomplexed oxazolidinone bromide suggest that complexation lowers the BDE due to the effect of the strong electron-withdrawing group on the C-Br bond dipole.
Feng
Hao
H
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA.
Kavrakova
Ivanka K
IK
Pratt
Derek A
DA
Tellinghuisen
Joel
J
Porter
Ned A
NA
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003500:Cyclization; D005609:Free Radicals / Q000737:chemistry; D006842:Hydrocarbons, Brominated / Q000138:chemical synthesis* / Q000737:chemistry*; D007202:Indicators and Reagents; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D009589:Nitrogen Oxides / Q000737:chemistry; D010080:Oxazoles / Q000138:chemical synthesis* / Q000737:chemistry*; D015018:Ytterbium / Q000737:chemistry
D000475:Alkenes; D005609:Free Radicals; D006842:Hydrocarbons, Brominated; D007202:Indicators and Reagents; D009589:Nitrogen Oxides; D010080:Oxazoles; D015018:Ytterbium