Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume -, Issue -, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202300895
Keywords
chiral phosphoric acid auxiliary catalyst; computational prediction; density functional theory; enantioconvergent synthesis; reaction mechanism
Categories
Ask authors/readers for more resources
Density functional theory computations provide mechanistic insights into Cu and chiral phosphoric acid (CPA) catalyzed enantioconvergent amination of racemic benzenesulfonohydrazide. The O-O bond homolysis of tert-butyl 4-phenylbutaneperoxoate is the turnover-limiting step with a total free energy barrier of 19.1 kcal/mol. Enantioconvergent amination is achieved by obtaining the same intermediate through a prochiral carbon atom. The order and mode of hydrogen atom transfer by CPA and tert-butyloxy significantly influence the enantioselectivity and energy barriers. The olefinic side product generated by beta-hydride elimination is thermodynamically less favorable by 9.9 kcal/mol. A series of phosphoric acids are predicted as promising co-catalysts with lower barriers for O-O bond homolysis.
Density functional theory computations reveal mechanistic insights into Cu and chiral phosphoric acid (CPA) catalyzed enantioconvergent amination of racemic benzenesulfonohydrazide. The O-O bond homolysis of tert-butyl 4-phenylbutaneperoxoate was found to be the turnover-limiting step with a total free energy barrier of 19.1 kcal/mol. The enantioconvergent amination is realized to obtain the same intermediate through prochiral carbon atom. The order and mode of hydrogen atom transferred by CPA and tert-butyloxy have a significant influence on the enantioselectivity and energy barriers. The olefinic side product generated by beta-hydride elimination is 9.9 kcal/mol thermodynamically less favourable. A series of phosphoric acids are predicted as promising co-catalysts with lower barriers for O-O bond homolysis.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available