posted on 2018-03-27, 00:00authored byKatrina
M. Mennie, Steven M. Banik, Elaine C. Reichert, Eric N. Jacobsen
The stereoselective synthesis of syn-β-fluoroaziridine
building blocks via chiral aryl iodide-catalyzed fluorination of allylic
amines is reported. The method employs HF–pyridine as a nucleophilic
fluoride source together with mCPBA as a stoichiometric
oxidant, and affords access to arylethylamine derivatives featuring
fluorine-containing stereocenters in high diastereo- and enantioselectivity.
Catalyst-controlled diastereoselectivity in the fluorination of chiral
allylic amines enabled the preparation of highly enantioenriched 1,3-difluoro-2-amines
bearing three contiguous stereocenters. The enantioselective catalytic
method was applied successfully to other classes of multifunctional
alkene substrates to afford anti-β-fluoropyrrolidines,
as well as a variety of 1,2-oxyfluorinated products.