Abstract:
Green Synthesis of Fluorinated Arenes, Benzoxazinones
and Benzamides
Three different types of reactions (Suzuki-Miyaura reaction, carbonylation reaction and
oxidation reaction) were employed to synthesize an assortment of diverse aromatic and
heterocyclic compounds. Fluorinated heterocycles are frequently found in
pharmaceuticals, drug candidates, ligands for transition metal catalysts and other molecular
functional materials, so efficient methods for the synthesis of these compounds are of
significant value. We described a selective strategy for the synthesis of poly-substituted
pyridines. The Suzuki-Miyaura reaction of 2,6-dichloro-3-(trifluoromethyl)pyridine with
one equivalent of aryl boronic acids resulted in site-selective formation of 2-aryl-6-chloro-
3-(trifluoromethyl)pyridine. Due to electronic reasons, the reaction takes place at the
sterically more hindered position. The reactions proceeded smoothly in the absence of
phosphine ligands.
A general and convenient methodology for 2-amino benzoxazinones synthesis has been
developed. Radially available 2-bromoanilines and isocyanates were used as substrates and
diverse products have been prepared in good yields. Notably, Mo(CO)6 as a solid CO
source was applied instead of gas.
x
A general procedure for oxidation of both benzyl alcohols and alkyl alcohols to primary
amides under catalyst free conditions has been developed. More than 25 examples of
primary amides were produced from their corresponding alcohols in moderate to excellent
yields. This is a practical procedure for primary amides synthesis, water and tert-butanol
are the only by-products.
