AUTHOR=Wang Xuerong , Sun Huilin , Li Caicui , Niu Shuijiao , Gao Yu , Chen Ying , Xu Tianwei , Wang Jinhui , Xu Huanjun 

TITLE=Catalytic Oxidative Cleavage of C(OH)-C Bonds in Lignin Model Compounds to Carboxylic Acids by Fe(NO3)3.9H2O/NaI/DMSO

JOURNAL=Frontiers in Chemistry

VOLUME=10

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.933763

DOI=10.3389/fchem.2022.933763

ISSN=2296-2646

ABSTRACT=<p>The secondary C(OH)-C bonds are abundant in biomass such as lignin and cellulose. Thus, selective cleavage of the C(OH)-C bonds into value chemicals attracted much attention. Molecular iodine has received considerable attention as an inexpensive and readily available catalyst to yield the corresponding products in excellent yields with high selectivity, but it is highly corrosive and toxic, making its use somewhat unattractive. In this study, I<sub>2</sub> was generated <italic>in situ</italic> from Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O/NaI, which was further combined with Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O to catalyze the oxidation process. In the reaction, the H<sub>2</sub>O molecule from the reaction and Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O attacked the phenylglyoxal to form benzaldehyde, which was further oxidized to benzoic acid. Aryl primary and secondary benzylic alcohols from lignin were successfully transformed into aryl carboxylic acids by Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O/NaI/DMSO. The catalytic system was green and efficient, avoiding the usage of toxic and corrosive molecular I<sub>2</sub>. From the experiments, it was clear that the yield of the product from the substrates with an electron-donating group was higher than that of electron-withdrawing substituted substrates, which was similar to the aryl secondary alcohols. Aryl alkyl ketones were also successfully conducted by the Fe(NO<sub>3</sub>)<sub>3</sub>.9H<sub>2</sub>O/NaI/DMSO catalytic system.</p>