Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides.

ABSTRACT: We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2,2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2,2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.

SUBMITTER: Mkrtchyan S

PROVIDER: S-EPMC8156957 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Photochemical (Hetero-)Arylation of Aryl Sulfonium Salts.

Project description:The construction of (hetero)biaryls, which are ubiquitous scaffolds among medical substances, functional materials, and agrochemicals, constitutes a key application of cross-coupling methods. However, these usually require multiple synthetic steps. Herein, we report a simple photoinduced and catalyst-free C-H/C-H (hetero)arylation cross-coupling through aryl thianthrenium salts, which are formed site-selectively by direct C-H functionalization. The key to this approach is the UV-light, which can disrupt the C-S bond to form thianthrene radical cations and aryl radicals.

| S-EPMC8383302 | biostudies-literature

Site-Selective C-H Oxygenation via Aryl Sulfonium Salts.

Project description:Herein, we report a two-step process forming arene C-O bonds in excellent site-selectivity at a late-stage. The C-O bond formation is achieved by selective introduction of a thianthrenium group, which is then converted into C-O bonds using photoredox chemistry. Electron-rich, -poor and -neutral arenes as well as complex drug-like small molecules are successfully transformed into both phenols and various ethers. The sequence differs conceptually from all previous arene oxygenation reactions in that oxygen functionality can be incorporated into complex small molecules at a late stage site-selectively, which has not been shown via aryl halides.

| S-EPMC7754133 | biostudies-literature

Aryl Sulfonium Salts for Site-Selective Late-Stage Trifluoromethylation.

Project description:Incorporation of the CF3 group into arenes has found increasing importance in drug discovery. Herein, we report the first photoredox-catalyzed cross-coupling of aryl thianthrenium salts with a copper-based trifluoromethyl reagent, which enables a site-selective late-stage trifluoromethylation of arenes. The reaction proceeds with broad functional group tolerance, even for complex small molecules on gram scale. The method was further extended to produce pentafluoroethylated derivatives.

| S-EPMC7754511 | biostudies-literature

Site-Selective Late-Stage Aromatic [18 F]Fluorination via Aryl Sulfonium Salts.

Project description:Site-selective functionalization of C-H bonds in small complex molecules is a long-standing challenge in organic chemistry. Herein, we report a broadly applicable and site-selective aromatic C-H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two-step C-H [18 F]fluorination of a series of marketed small-molecule drugs.

| S-EPMC7004179 | biostudies-literature

Late-Stage Heteroarylation of Hetero(aryl)sulfonium Salts Activated by α-Amino Alkyl Radicals.

Project description:We report a late-stage heteroarylation of aryl sulfonium salts through activation with α-amino alkyl radicals in a mechanistically distinct approach from previously reported halogen-atom transfer (XAT). The new mode of activation of aryl sulfonium salts proceeds in the absence of light and photoredox catalysts, engaging a wide range of hetarenes. Furthermore, we demonstrate the applicability of this methodology in synthetically useful cross-coupling transformations.

| S-EPMC8251951 | biostudies-literature

Enantioselective and Regiodivergent Copper-Catalyzed Electrophilic Arylation of Allylic Amides with Diaryliodonium Salts.

Project description:A catalytic enantioselective and regiodivergent arylation of alkenes is described. Chiral copper(II)bisoxazoline complexes catalyze the addition of diaryliodonium salts to allylic amides in excellent ee. Moreover, the arylation can be controlled by the electronic nature of the diaryliodonium salt enabling the preparation of nonracemic diaryloxazines or β,β'-diaryl enamides.

| S-EPMC4569064 | biostudies-literature

A General and Practical Palladium-Catalyzed Direct ?-Arylation of Amides with Aryl Halides.

Project description:An efficient system for the direct catalytic intermolecular ?-arylation of acetamide derivatives with aryl bromides and chlorides is presented. The palladium catalyst is supported by Kwong's indole-based phosphine ligand and provides monoarylated amides in up to 95% yield. Excellent chemoselectivities (>10:1) in the mono- and diarylation with aryl bromides were achieved by careful selection of bases, solvents, and stoichiometry. Under the coupling conditions, the weakly acidic ?-protons of amides (pKa up to 35) were reversibly depotonated by LiO t Bu, NaO t Bu, or NaN(SiMe3)2.

| S-EPMC3994175 | biostudies-literature

2,4-Difluoro-phenyl-boronic acid.

Project description:The mol-ecular structure of the title compound, C(6)H(5)BF(2)O(2), is essentially planar (mean deviation = 0.019?Å), indicating electronic delocalization between the dihydroxy-boryl group and the aromatic ring. In the crystal structure, inversion dimers linked by two O-H?O hydrogen bonds arise. An intra-molecular O-H?F hydrogen bond reinforces the conformation and the same H atom is also involved in an inter-molecular O-H?F link, leading to mol-ecular sheets in the crystal.

| S-EPMC2967960 | biostudies-literature

Synthesis of C?-Symmetric Benzimidazolium Salts and Their Application in Palladium-Catalyzed Enantioselective Intramolecular ?-Arylation of Amides.

Project description:A series of C?-symmetric chiral benzimidazolium salts, the precursor of N-heterocyclic carbene ligands, were designed and synthesized from 1,2-dibromobenzene. In situ prepared corresponding carbenes were tested in the asymmetric palladium-catalyzed intramolecular ?-arylation of amides, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

| S-EPMC6274209 | biostudies-literature

Accessing 2,1-borazaronaphthols: self-arylation of 1-alkyl-2-aryl-3-bromo-2,1-borazaronaphthalenes.

Project description:Unlike their B-alkyl counterparts, brominated N-alkyl B-aryl 2,1-borazaronaphthalenes undergo a self-arylation reaction in the presence of a catalytic amount of palladium and base, in which the azaborine serves as both the electrophile and the nucleophile. The products of the self-arylation are air- and moisture-stable 2,1-borazaronaphthols, previously only observed in basic alcoholic solvents. The steric encumbrance of the azaborine appears to prevent formation of the corresponding boron acid anhydride, allowing access to a family of 2,1-borazaronaphthol derivatives.

| S-EPMC4156240 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data