Open AccessOne‐Pot Synthesis of 2,5‐Furandicarboxylic Acid from 2‐Furoic Acid by a Pd‐catalyzed Bromination–Hydroxycarbonylation Tandem Reaction in Acetate Buffer
Author(s) -
Yao YinQing,
Zhao KaiChun,
Zhuang YiYing,
Chen XiaoChao,
Lu Yong,
Liu Ye
Publication year - 2022
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202100301
Subject(s) - halogenation , chemistry , catalysis , tandem , reagent , organic chemistry , yield (engineering) , combinatorial chemistry , materials science , metallurgy , composite material
The one‐pot synthesis of 2,5‐furandicarboxylic acid from 2‐furoic acid with a yield of 57 % was achieved for the first time using a Pd‐catalyzed bromination‐hydroxycarbonylation tandem reaction in HOAc‐NaOAc buffer. This synthetic protocol shows major improvements compared to previously reported methods, such as using biomass‐based 2‐furoic acid as low‐cost raw material, one‐pot synthesis without isolation of intermediate products, and no need for an acidification procedure. Experiments indicate that the involved Xantphos‐modified Pd‐catalyst and the buffer solution play significant promoting roles for each individual reaction whereas Br 2 (as the brominating reagent) had a negative effect on the second hydroxycarbonylation step, while CO was deleterious for the first bromination step. Hence, in this practical one‐pot synthesis, Br 2 should be consumed in the first bromination step as fully as possible, and CO is introduced after the first bromination step has been completed.