DTBP-promoted site-selective α-alkoxyl C-H functionalization of alkyl esters: synthesis of 2-alkyl ester substituted chromanones.

Org Biomol Chem

School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, Changzhou University, Changzhou 213164, P. R. China. and School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001, P. R. China.

Published: May 2021

The direct C-H functionalization of ethyl acetates was developed, delivering a variety of 1-(4-oxochroman-2-yl)ethyl acetate derivatives by reacting with chromones. This reaction has a wide substrate scope with excellent site-selective C-H activation at the inactive α-hydrogen of the alkoxyl group instead of the α-hydrogen of the carbonyl group under radical conditions. Compared with other protocols for the α-alkoxyl C-H functionalization of alkyl esters, a distinguishing feature of this reaction is that no metal catalyst was required, with DTBP as the sole oxidant.

Download full-text PDF

Source
http://dx.doi.org/10.1039/d1ob00605cDOI Listing

Publication Analysis

Top Keywords

c-h functionalization
12
α-alkoxyl c-h
8
functionalization alkyl
8
alkyl esters
8
dtbp-promoted site-selective
4
site-selective α-alkoxyl
4
c-h
4
esters synthesis
4
synthesis 2-alkyl
4
2-alkyl ester
4

Similar Publications

Late-stage C-H trifluoroacetylation of quinoxaline-2(1)-ones using masked trifluoroacyl reagents.

Org Biomol Chem

January 2025

Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing 210095, P. R. China.

A strategy for trifluoroacetylation of quinoxaline-2(1)-ones has been investigated. This strategy employs masked trifluoroacyl reagents to obtain trifluoroacetylated quinoxaline-2(1)-ones under metal-, catalyst-, and light-free conditions. This approach is distinguished by its functional group compatibility and tolerance, as well as the simplicity of the experimental process, making it suitable for gram-scale synthesis.

View Article and Find Full Text PDF

Divergent roles of mA in orchestrating brown and white adipocyte transcriptomes and systemic metabolism.

Nat Commun

January 2025

Section of Islet Cell and Regenerative Biology, Joslin Diabetes Center; Department of Medicine, BIDMC; Harvard Stem Cell Institute, Harvard Medical School, Boston, MA, USA.

N-methyladenosine (mA) is among the most abundant mRNA modifications, yet its cell-type-specific regulatory roles remain unclear. Here we show that mA methyltransferase-like 14 (METTL14) differentially regulates transcriptome in brown versus white adipose tissue (BAT and WAT), leading to divergent metabolic outcomes. In humans and mice with insulin resistance, METTL14 expression differs significantly from BAT and WAT in the context of its correlation with insulin sensitivity.

View Article and Find Full Text PDF

Regioselective Difluoroalkylation of 2-Pyridones with Fluoroalkyl Bromides Enabled by a Nickel(II) Catalyst.

Chem Asian J

January 2025

National Chemical Laboratory CSIR, Chemical Engineering Division, Dr. Homi Bhabha Road, 411008, Pune, INDIA.

Regioselective C-H difluoroalkylation of diverse 2-pyridones with ethyl bromodifluoroacetates and bromodifluoroacetamides is accomplished by using a (dppf)NiCl2 catalyst under mild conditions. This efficient protocol could deliver a variety of C-3 difluoroalkylated pyridones with the tolerance of a range of highly susceptible functionalities, such as -Cl, -Br, -I, -COMe, -CN, -NMe2 and -NO2, including heteroarenes like pyridinyl, furanyl, thiophenyl and carbazolyl moieties. A preliminary mechanistic study suggests the radical pathway for the reaction involving fluoroalkyl radical intermediate.

View Article and Find Full Text PDF

Even though α-arylation of ketones is attractive for direct C-H functionalization of organic substrates, the method largely relies on phosphine-ligated palladium complexes. Only recently, efforts have focused on developing nitrogen-based ligands as a more sustainable alternative to phosphines, with pyridine-functionalized pyridinium amidate (pyr-PYA) ,'-bidentate ligands displaying good selectivity and activity. Here, we report on a second generation set of catalyst precursors that feature a 5-membered N-heterocycle instead of a pyridine as chelating unit of the PYA ligand to provide less steric congestion for the rate-limiting transmetalation of the enolate.

View Article and Find Full Text PDF

Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids and ferritin offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C-H hydrogen bonds.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!