Controllable C-H Alkylation of Polyethers via Iron Photocatalysis

Zhang, Zongnan1; Li, Xinyang1; Zhou, Dezhong1; Ding, Shujiang1; Wang, Minyan2; Zeng, Rong1,3

2023-03-01

10.1021/jacs.3c01100

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

The efficient conversion of a C-H bond in the polyether chain to other functional groups provides great opportunities for development of novel applications in many research fields. However, this field is quite underdeveloped due to the key challenge on controlling the selectivity of the C-H bond functionalization over the chain cleavage. In this work, we report a controllable C-H bond alkylation of polyethers under mild conditions via photoinduced iron catalysis. The level of functionalization could be controlled by using different amounts of alkenes and various reaction times, while the molecular weight distributions were maintained narrow. A broad scope of electron-deficient alkenes containing nitrile, ester, epoxide, terminal alkynyl, 2,5-dioxotetrafuranyl, and 2,5-dioxopyrrolidinyl groups could be utilized to functionalize the different polyethers with great efficiencies. The potential applications of the modified polyethylene glycols and polyethylene oxides were explored by the preparation of novel hydrogels and solid-state electrolytes with enhancement of lithium ion conductivities. Moreover, the density functional theory calculation disclosed the plausible mechanism and explained the high selectivity for the C- H alkylation.

SCI ; EI ; CCR

英语

NI论文

通讯

National Natural Science Foundation of China[21901197] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; National Key R&D Program of China[2022YFA1503200]

Chemistry

Chemistry, Multidisciplinary

WOS:000959604500001

AMER CHEMICAL SOC

20231413828389

Catalysis ; Catalyst activity ; Chemical bonds ; Density functional theory ; Ethers ; Iron ; Molecular weight distribution ; Olefins ; Polyethylene glycols ; Polyethylene oxides ; Polyethylenes ; Solid electrolytes

Iron:545.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Organic Polymers:815.1.1 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Xi An Jiao Tong Univ, Sch Chem, Sch Chem Engn & Technol, Xian 710049, Peoples R China
2.Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing 210093, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Guangzhou 518055, Peoples R China

Zhang, Zongnan,Li, Xinyang,Zhou, Dezhong,et al. Controllable C-H Alkylation of Polyethers via Iron Photocatalysis[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(13):7612-7620.

Zhang, Zongnan,Li, Xinyang,Zhou, Dezhong,Ding, Shujiang,Wang, Minyan,&Zeng, Rong.(2023).Controllable C-H Alkylation of Polyethers via Iron Photocatalysis.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(13),7612-7620.

Zhang, Zongnan,et al."Controllable C-H Alkylation of Polyethers via Iron Photocatalysis".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.13(2023):7612-7620.