Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials

Shi，Yang1; Yang，Ge1; Shen，Boming2; Yang，Yudong1; Yan，Lipeng1; Yang，Feng1; Liu，Jiahui1; Liao，Xingrong1; Yu，Peiyuan2; Bin，Zhengyang1; You，Jingsong1

2021

10.1021/jacs.1c11277

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

The installation of (benzo)thiophene-containing biaryls via coupling reactions has become a staple in designing photoelectric materials. Undeniably, C-H/C-H cross-coupling reactions between two (hetero)aromatics would be a shortcut toward these structural fragments. While more reliable cross-coupling technologies are well-established to provide C2-arylated (benzo)thiophenes, efficient methods that arylate the C3-position remain underdeveloped. Herein we provide insight into the factors that determine regioselectivity switching for these cross-coupling reactions. X-ray crystallographic analysis gives solid evidence for the key roles of triflate in regioselective dearomatization and acetate in base-assisted anti-β-deprotonated rearomatization. The first isolation and X-ray characterization of a medium-sized dearomatized cyclometalated adduct involving both substrates provide extra insight into aerobic oxidative Ar-H/Ar-H cross-coupling reactions. The mechanistic breakthrough incubates the first example, enabling C-H/C-H-type C3-arylation of benzothiophenes. Finally, this chemistry is used to design blue-emitting thermally activated delayed fluorescence (TADF) materials with a helicene conformation that exhibit a high maximum external quantum efficiency of 25.4% in OLED.

EI

英语

NI期刊

其他

20215011317914

Chemical bonds ; Fluorescence ; Organic light emitting diodes (OLED) ; Photoelectricity ; Regioselectivity ; X ray crystallography

Electricity: Basic Concepts and Phenomena:701.1 ; Semiconductor Devices and Integrated Circuits:714.2 ; Light/Optics:741.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Crystal Lattice:933.1.1

2-s2.0-85120883131

Scopus

1.Key Laboratory of Green Chemistry and Technology of Ministry of Education,College of Chemistry,Sichuan University,Chengdu,29 Wangjiang Road,610064,China
2.Department of Chemistry and Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,518055,China

Shi，Yang,Yang，Ge,Shen，Boming,et al. Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials[J]. Journal of the American Chemical Society,2021,143.

Shi，Yang.,Yang，Ge.,Shen，Boming.,Yang，Yudong.,Yan，Lipeng.,...&You，Jingsong.(2021).Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials.Journal of the American Chemical Society,143.

Shi，Yang,et al."Insight into Regioselective Control in Aerobic Oxidative C-H/C-H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials".Journal of the American Chemical Society 143(2021).