Synergetic copper/TEMPO-catalysed benzylic C–H imidation with N-fluorobenzenesulfonimide at room temperature and tandem conversions with alcohols or arenes

Published on Jun 29, 2021in Organic chemistry frontiers5.155
· DOI :10.1039/D1QO00340B
Zhong Shao1
Estimated H-index: 1
,
Fang Wang3
Estimated H-index: 3
+ 2 AuthorsZiyuan Li11
Estimated H-index: 11
(Sichuan University)
Source
Abstract
📖 Papers frequently viewed together
36 Citations
10 Citations
References96
Newest
#1Mohamad Sabbah (University of Cambridge)H-Index: 4
#2Vitor Mendes (University of Cambridge)H-Index: 17
Last. Chris Abell (University of Cambridge)H-Index: 74
view all 10 authors...
Tuberculosis (TB) remains a leading cause of mortality amongst infectious diseases worldwide. InhA, an enoyl ACP-reductase, has been the focus of numerous drug discovery efforts as this is the targ...
10 CitationsSource
#1Huayou Hu (UW: University of Wisconsin-Madison)H-Index: 1
#2Si Jie Chen (UW: University of Wisconsin-Madison)H-Index: 2
Last. Shannon S. Stahl (UW: University of Wisconsin-Madison)H-Index: 102
view all 8 authors...
Cross-coupling reactions enable rapid, convergent synthesis of diverse molecules and provide the foundation for modern chemical synthesis. The most widely used methods employ sp2-hybridized coupling partners, such as aryl halides or related pre-functionalized substrates. Here, we demonstrate copper-catalysed oxidative cross-coupling of benzylic C–H bonds with alcohols to afford benzyl ethers, enabled by a redox buffering strategy that maintains the activity of the copper catalyst throughout the ...
29 CitationsSource
#1Muhammet Uyanik (Nagoya University)H-Index: 21
#2Kohei Nishioka (Nagoya University)H-Index: 2
Last. Kazuaki Ishihara (Nagoya University)H-Index: 80
view all 4 authors...
ortho-Quinone methides are useful transient synthetic intermediates in organic synthesis. These species are most often generated in situ by the acid- or base-mediated transformation of phenols that have been pre-functionalized at a benzylic position, or by biomimetic oxidation of the corresponding ortho-alkylphenols with metal oxidants or transition-metal complexes. Here we describe a method for the transition-metal-free oxidative generation of o-QMs from ortho-alkylarenols, using hypoiodite cat...
23 CitationsSource
#1Byung Joo Lee (UW: University of Wisconsin-Madison)H-Index: 3
#2Kimberly S. DeGlopper (UW: University of Wisconsin-Madison)H-Index: 1
Last. Tehshik P. Yoon (UW: University of Wisconsin-Madison)H-Index: 50
view all 3 authors...
Methods that enable the direct C-H alkoxylation of complex organic molecules are significantly underdeveloped, particularly in comparison to analogous strategies for C-N and C-C bond formation. In particular, almost all methods for the incorporation of alcohols by C-H oxidation require the use of the alcohol component as a solvent or co-solvent. This condition limits the practical scope of these reactions to simple, inexpensive alcohols. Reported here is a photocatalytic protocol for the functio...
30 CitationsSource
#1Mitsuyasu Kawaguchi (Nagoya City University)H-Index: 11
#2Xiang Han (Nagoya City University)H-Index: 1
Last. Hidehiko Nakagawa (Nagoya City University)H-Index: 32
view all 9 authors...
Ectonucleotide pyrophosphatase/phosphodiesterase 1 (ENPP1) is a type II transmembrane glycoprotein that is involved in bone metabolism and insulin resistance, hydrolyzes 2′,3′-cGAMP (a STING ligand that promotes innate immunity), and is associated with cancer stemness in breast cancers and glioblastoma. Therefore, ENPP1 is considered a candidate therapeutic target and/or biomarker for early diagnosis of malignant tumors. In this study, we designed and synthesized a sensitive ENPP1 fluorescence p...
11 CitationsSource
#1Fengyu Bao (Henan Agricultural University)H-Index: 1
#2Yuanbo Cao (Henan Agricultural University)H-Index: 1
Last. Junhao Zhu (Henan Agricultural University)H-Index: 1
view all 4 authors...
Direct conversion of cheap methylarenes to benzylic amines, which are essential structural units of important drugs, is of great significance. However, the known methodologies suffer from the requirement of noble metal catalysts, heavy metal residues or strong oxidants. Herein, the first biocompatible iron-catalyzed benzylic C (sp3)–H amination of methylarenes with N-fluorobenzenesulfonimide is described. The reactions of methylarenes bearing electron-donating groups and electron-withdrawing gro...
7 CitationsSource
#1Qi Miao (Sichuan University)H-Index: 3
#2Zhong Shao (Sichuan University)H-Index: 1
Last. Ziyuan Li (Sichuan University)H-Index: 11
view all 8 authors...
A TEMPO-catalysed direct amination of arene through C–H bond cleavage employing N-fluorobenzenesulfonimide (NFSI) as the amination reagent in good to excellent yields with broad arene scope in the absence of any metal, ligand or additive is reported. Unlike previous transition metal-catalysed aminations in which high reaction temperatures are usually necessary, this novel reaction at room temperature is the first example of C–H amination with NFSI that is realised via organocatalysis. The probab...
11 CitationsSource
#1Yang Yu (DUT: Dalian University of Technology)H-Index: 3
#2Gen Luo (DUT: Dalian University of Technology)H-Index: 13
Last. Yi Luo (DUT: Dalian University of Technology)H-Index: 26
view all 4 authors...
Theoretical calculations have been performed to gain deeper understanding on the mechanism of Cp*Co(III)-catalysed C(sp3)–H amination of 8-methylquinoline with phenyl-1,4,2-dioxazol-5-one. The result suggests that the additive AgSbF6 could thermodynamically facilitate the generation of catalytically active species Cp*Co(OPiv)+. The subsequent catalytic cycle involves sequential external base assisted C(sp3)–H activation, decarboxylation, nitrene insertion, and protonation. Importantly, a remarka...
9 CitationsSource
#1Parthasarathy Gandeepan (GAU: University of Göttingen)H-Index: 31
#2Thomas Müller (GAU: University of Göttingen)H-Index: 5
Last. Lutz Ackermann (GAU: University of Göttingen)H-Index: 125
view all 6 authors...
C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for...
816 CitationsSource
#1Bowen Lei (Sichuan University)H-Index: 6
#2Qi Miao (Sichuan University)H-Index: 3
Last. Ziyuan Li (Sichuan University)H-Index: 11
view all 7 authors...
A novel efficient metal-free aminoiodination of alkenes with N-fluorobenzenesulfonimide (NFSI) through an iodonium intermediate under mild conditions with good regioselectivity and stereoselectivity is reported. Unlike transition-metal catalysed aminative bisfunctionalization with NFSI in which the oxidative addition of NFSI to transition-metals affords an electrophilic amino radical, the oxidation of anionic iodide by NFSI in situ generates an electrophilic iodine cation and an amino nucleophil...
11 CitationsSource
Cited By1
Newest
#1Dong Yang (Sichuan University)H-Index: 1
#2Jiaming Chen (Sichuan University)
Last. Ziyuan Li (Sichuan University)H-Index: 11
view all 8 authors...
Source