Ultrafine Copper Oxide Particles Dispersed on Nitrogen‐Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass‐Derived 5‐Hydroxymethylfurfural

One‐pot synthesis of furan‐2,5‐dimethylcarboxylate (FDMC) from 5‐hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen‐doped hollow carbon nanospheres (CuO/N−C−HNSs) as a catalyst and tert ‐butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N−C−HNSs was prepared through a template protection‐sacrifice strategy using SiO 2 as a sacrificial template and histidine as the precursor for N and C. N‐doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m 2 /g, the CuO/N−C−HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP 3 C−H bond functionalization is also demonstrated using the same catalyst.