Arylation of Diethyl Acetamidomalonate with Diaryliodonium Salts En Route to α-Arylglycines.

Diethyl acetamidomalonate (DEAM) has been widely used for the synthesis of α-amino acids via C-alkylation under basic conditions followed by hydrolysis/decarboxylation. In contrast, the C-arylation of this reagent remains undeveloped. Herein, we report a novel strategy for the synthesis of racemic α-arylglycines based on the selective arylation of DEAM with diaryliodonium salts under mild, transition metal-free conditions. The reaction features good functional group tolerance and easy scalability and is applicable to the chemoselective C-H-modification of arenes including approved drugs, thus enabling a straightforward approach to complex α-arylglycines that would be challenging to make otherwise.

Synthesis of Quinoline-2-thiones by Selective Deoxygenative C-H/C-S Functionalization of Quinoline N-Oxides with Thiourea.

Quinoline-2-thiones valuable for synthetic and medicinal chemistry applications were obtained with excellent regioselectivity employing a deoxygenative C-H functionalization of readily available quinoline-N-oxides with thiourea upon activation with triflic anhydride. Unlike the current methods, this approach provides general access to diverse quinoline-2-thiones functionalized with groups of different electronic natures. Experimental simplicity and good to high yields are advantages of this protocol. Given the high reactivity of quinoline-2-thiones, this method provides an entry point for the synthesis of diverse organosulfur quinoline scaffolds.