Highly Efficient and Selective N-Formylation of Amines with CO₂ and H₂ Catalyzed by Porous Organometallic Polymers

TY - JOUR

T1 - Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers

AU - Shen, Yajing

AU - Zheng, Qingshu

AU - Chen, Zhe Ning

AU - Wen, Daheng

AU - Clark, James Hanley

AU - Xu, Xin

AU - Tu, Tao

PY - 2021/2/19

Y1 - 2021/2/19

N2 - The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.

AB - The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.

U2 - 10.1002/anie.202011260

DO - 10.1002/anie.202011260

M3 - Article

SN - 1433-7851

VL - 60

SP - 4125

EP - 4132

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 8

ER -