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 (sp)-H amination of methylarenes with -fluorobenzenesulfonimide is described. The reactions of methylarenes bearing electron-donating groups and electron-withdrawing groups ran smoothly under ligand and additional oxidant free conditions. Both toluene derivatives and 8-methylquinoline can be aminated by the same iron catalyst.
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http://dx.doi.org/10.1039/c9ra05294a | DOI Listing |
J Am Chem Soc
September 2024
Department of Biopharmaceutics, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.
Primary amines are privileged molecules in drug development. Yet, there is a noticeable scarcity of methods for directly introducing a primary amine group into the ubiquitous C(sp)-H bonds within organic compounds. Here, we report an iron-based catalytic system that enables direct primary amination of C(sp)-H bonds under aqueous conditions and air.
View Article and Find Full Text PDFJ Org Chem
November 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha, PIN 752050, India.
The utilization of earth-abundant, cheap, and nontoxic transition metals in important catalytic transformations is essential for sustainable development, and iron has gained significant attention as the most abundant transition metal. A mixture of FeCl (3 mol %), phenanthroline (6 mol %), and KOBu (0.4 eqivalent) was used as an effective catalyst for the sp C-H alkylation of fluorene using alcohol as a nonhazardous alkylating partner, and eco-friendly water was formed as the only byproduct.
View Article and Find Full Text PDFChem Commun (Camb)
May 2024
College of Medicine, Jiaxing University, 118 Jiahang Road, Jiaxing, 314001, P. R. China.
Here, we describe an iron-catalyzed benzylic C-H thiolation of alkylarenes photoinduced ligand-to-metal charge-transfer. The protocol features operational simplicity, mild reaction conditions, and the use of FeCl as catalyst and thiols/disulfides as sulfur sources, which enables the transformation of diverse benzylic C-H bonds into C-S bonds with a high efficiency.
View Article and Find Full Text PDFOrg Lett
April 2024
Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Botanic Garden, Howrah 711103, India.
An oxygen-dependent ligand-controlled chemoselective synthesis of vinyl nitriles and -olefins by coupling a variety of alcohols and benzyl cyanides, catalyzed by a well-characterized, air-stable, easy-to-prepare Fe(II) catalyst () bearing a redox-active arylazo pincer () is reported. The azo-moiety of the ligand backbone acts as an electron and hydrogen reservoir, enabling catalyst to efficiently produce a broad spectrum of vinyl nitriles and -olefins in moderate to good yields selectively under an oxygen and argon atmosphere, respectively.
View Article and Find Full Text PDFChem Commun (Camb)
March 2024
Laboratoire d'Innovation Moléculaire et Applications (LIMA), UMR 7042, Université de Strasbourg/Université de Haute-Alsace/CNRS, ECPM, 25 rue Becquerel, 67087, Strasbourg, France.
Access to ,-glycosyl amino acids as a novel class of glycomimetics is reported by means of radical generation, intermolecular addition and stereoselective reduction a metal-induced hydrogen atom transfer (MHAT) sequence. The 'matched' coupling of -D-glycals with an enantiopure dehydroalanine bearing a ()-configured benzyl oxazolidinone enables a singular case of two-fold diastereocontrol under iron catalysis. In the common -D-glucal series, the nature of the C-2 substituent was found to play a key role from both reactivity and stereocontrol aspects.
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