Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Sterically Congested 2,6-Disubstituted Anilines from Direct C-N Bond Formation at an Iodine(III) Center.

ABSTRACT: 2,6-Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(III) center. The efficiency of the coupling procedure is further demonstrated within the short synthesis of a chemerin binding inhibitor.

SUBMITTER: Lucchetti N

PROVIDER: S-EPMC5113687 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Sterically Congested 2,6-Disubstituted Anilines from Direct C-N Bond Formation at an Iodine(III) Center.

Lucchetti Nicola N Scalone Michelangelo M Fantasia Serena S Muñiz Kilian K

Angewandte Chemie (International ed. in English) 20161001 42

2,6-Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(III) center. The efficiency of the coupling procedure is further demonstrated within the short synthesis ...[more]

PMID: 27651117

Similar Datasets

Crystal structures of three sterically congested disilanes.

Project description:In the three sterically congested silanes, C24H38Si2 (1) (1,1,2,2-tetra-isopropyl-1,2-di-phenyl-disilane), C24H34Br4Si2 (2) [1,1,2,2-tetra-kis-(2-bromo-propan-2-yl)-1,2-di-phenyl-disilane] and C32H38Si2 (3) (1,2-di-tert-butyl-1,1,2,2-tetra-phenyl-disilane), the Si-Si bond length is shortest in (1) and longest in (2), with (3) having an inter-mediate value, which parallels the increasing steric congestion. A comparison of the two isopropyl derivatives, (1 and 2), shows a significant increase in the Si-C(ipso) distance with the introduction of bromine. Also, in the brominated compound 2, attractive inter-molecular Br⋯Br inter-actions exist with Br⋯Br separations ca 0.52 Å shorter than the sum of the van der Waals radii. In compound 2, one of the bromo-isopropyl groups is rotationally disordered in an 0.8812 (9):0.1188 (9) ratio. Compound 3 exhibits 'whole mol-ecule' disorder in a 0.9645 (7):0.0355 (7) ratio with the Si-Si bonds in the two components making an angle of ca 66°.

| S-EPMC5347074 | biostudies-literature

Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors.

Project description:"Hypervalent" iodine(III) derivatives have been established as powerful reagents in organic transformations, but so far only a handful of studies have addressed their potential use as halogen-bonding noncovalent Lewis acids. In contrast to "classical" halogen-bond donors based on iodine(I) compounds, iodine(III) salts feature two directional electrophilic axes perpendicular to each other. Herein we present the first systematic investigation on biaxial binding to such Lewis acids in solution. To this end, hindered and unhindered iodolium species were titrated with various substrates, including diesters and diamides, via 1H NMR spectroscopy and isothermal titration calorimetry. Clear evidence for biaxial binding was obtained in two model systems, and the association strengths increased by 2 orders of magnitude. These findings were corroborated by density functional theory calculations (which reproduced the trend well but underestimated the absolute binding constants) and a cocrystal featuring biaxial coordination of a diamide to the unhindered iodolium compound.

| S-EPMC7252947 | biostudies-literature

Construction of sterically congested oxindole derivatives <i>via</i> visible-light-induced radical-coupling.

Project description:The oxindole scaffold represents an important structural feature in many natural products and pharmaceutically relevant molecules. Herein, we report a visible-light-induced modular methodology for the synthesis of complex 3,3'-disubstituted oxindole derivatives. A library of valuable fluoroalkyl-containing highly sterically congested oxindole derivatives can be synthesized by a catalytic three-component radical coupling reaction under mild conditions (metal & photocatalyst free, >80 examples). This strategy shows high functional group tolerance and broad substrate compatibility (including a wide variety of terminal or non-terminal alkenes, conjugated dienes and enynes, and a broad array of polyfluoroalkyl iodide and oxindoles), which enables modular modification of complex drug-like compounds in one chemical step. The success of solar-driven transformation, large-scale synthesis, and the late-stage functionalization of bioactive molecules, as well as promising tumor-suppressing biological activities, highlights the potential for practical applications of this strategy. Mechanistic investigations, including a series of control experiments, UV-vis spectroscopy and DFT calculations, suggest that the reaction underwent a sequential two-step radical-coupling process and the photosensitive perfluoroalkyl benzyl iodides are key intermediates in the transformation.

| S-EPMC8635216 | biostudies-literature

Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts.

Project description:A variety of novel imidazolidinone-based organocatalysts with bulky substituents were synthesized under mild reaction conditions starting from easily accessible substrates. Different natural and unnatural amino acid methyl amides were cyclized with aromatic carbaldehydes to yield two diastereomeric MacMillan-type catalysts. Special emphasis was put on bulky residues such as mesityl and pyrene moieties.

| S-EPMC5727825 | biostudies-literature

Synthesis of 2,6-disubstituted tetrahydroazulene derivatives.

Project description:Synthesis of hydroazulene derivatives has been carried out through a ring-enlargement route by using carbene adduct intermediates. The protocol can be applied for the construction of functionalized hydroazulene skeletons as key components of many natural products as well as the core system of novel liquid-crystalline materials.

| S-EPMC3388855 | biostudies-literature

A Concise Route to Water-Soluble 2,6-Disubstituted BODIPY-Carbohydrate Fluorophores by Direct Ferrier-Type C-Glycosylation.

Project description:Novel, linker-free, BODIPY-carbohydrate derivatives containing sugar residues at positions C2 and C6 are efficiently obtained by, hitherto unreported, Ferrier-type C-glycosylation of 8-aryl-1,3,5,7-tetramethyl BODIPYs with commercially available tri-O-acetyl-d-glucal followed by saponification. This transformation, which involves the electrophilic aromatic substitution (SEAr) of the dipyrrin framework with an allylic oxocarbenium ion, provides easy access to BODIPY-carbohydrate hybrids with excellent photophysical properties and a weaker tendency to aggregate in concentrated water solutions.

| S-EPMC8279486 | biostudies-literature

Borylation directed borylation of N-alkyl anilines using iodine activated pyrazaboles.

Project description:Doubly electrophilic pyrazabole derivatives (pyrazabole = [H2B(μ-C3N2H3)]2) combined with one equiv. of base effect the ortho-borylation of N-alkyl anilines. Initial studies found that the bis(trifluoromethane)sulfonimide ([NTf2]-) pyrazabole derivative, [H(NTf2)B(μ-C3N2H3)]2, is highly effective for ortho-borylation, with this process proceeding through N-H borylation and then ortho C-H borylation. The activation of pyrazabole by I2 was developed as a cheaper and simpler alternative to using HNTf2 as the activator. The addition of I2 forms mono or ditopic pyrazabole electrophiles dependent on stoichiometry. The ditopic electrophile [H(I)B(μ-C3N2H3)]2 was also effective for the ortho-borylation of N-alkyl-anilines, with the primary C-H borylation products readily transformed into pinacol boronate esters (BPin) derivatives. Comparison of borylation reactions using the di-NTf2-and the diiodo-pyrazabole congeners revealed that more forcing conditions are required with the latter. Furthermore, the presence of iodide leads to competitive formation of side products, including [HB(μ-C3N2H3)3BH]+, which are not active for C-H borylation. Using [H(I)B(μ-C3N2H3)]2 and 0.2 equiv. of [Et3NH][NTf2] combines the higher yields of the NTf2 system with the ease of handling and lower cost of the iodide system generating an attractive process applicable to a range of N-alkyl-anilines. This methodology represents a metal free and transiently directed C-H borylation approach to form N-alkyl-2-BPin-aniline derivatives.

| S-EPMC10631245 | biostudies-literature

Bulky 2,6-disubstituted aryl siloxanes and a disilanamine.

Project description:The crystal structures of 5-bromo-1,3-di-tert-butyl-2-[(tri-methyl-sil-yl)-oxy]benzene, C17H29BrOSi, (I), 1,3-di-tert-butyl-2-[(tri-methyl-sil-yl)-oxy]benzene, C17H30OSi, (II), and N-(2,6-diiso-propyl-phen-yl)-1,1,1-trimethyl-N-(tri-methyl-sil-yl)silanamine, C18H35NSi2, (III), are reported. Compound (I) crystallizes in space group P21/c with Z' = 1, (II) in Pnma with Z' = 0.5 and (III) in Cmcm with Z' = 0.25. Consequently, the mol-ecules of (II) are constrained by m and those of (III) by m2m site symmetries. Despite this, both (I) and (II) are distorted towards mild boat conformations, as is typical of 2,6-di-tert-butyl-substituted phenyl compounds, reflecting the high local steric pressure of the flanking alkyl groups. Compound (III) by contrast is planar and symmetric, and this lack of distortion is compatible with the lower steric pressure of the flanking 2,6-diisopropyl substituents.

| S-EPMC7057366 | biostudies-literature

Direct amination of ?-halo-?-ketoesters with anilines.

Project description:The direct amination of ?-haloacetoacetates with anilines is described. Compared to existing methods, this simple protocol provides an attractive strategy to prepare diverse ?-anilino-?-ketoesters in one step. Good to excellent yields of the amination products were obtained under robust conditions, providing versatile and useful scaffolds.

| S-EPMC3321089 | biostudies-literature

Direct sulfonylation of anilines mediated by visible light.

Project description:Sulfones feature prominently in biologically active molecules and are key functional groups for organic synthesis. We report a mild, photoredox-catalyzed reaction for sulfonylation of aniline derivatives with sulfinate salts, and demonstrate the utility of the method by the late-stage functionalization of drugs. Key features of the method are the straightforward generation of sulfonyl radicals from bench-stable sulfinate salts and the use of simple aniline derivatives as convenient readily available coupling partners.

| S-EPMC5868301 | 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