Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Molander GA

PROVIDER: S-EPMC4156240 | biostudies-literature | 2014 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

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

Molander Gary A GA Wisniewski Steven R SR

The Journal of organic chemistry 20140818 17

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 a ...[more]

PMID: 25133658

Similar Datasets

Reductive cross-coupling of 3-bromo-2,1-borazaronaphthalenes with alkyl iodides.

Project description:Conditions have been developed for the reductive cross-coupling of 3-bromo-2,1-borazaronaphthalenes with primary and secondary alkyl iodides. This method allows direct alkylation of azaborine cores, providing efficient access to functionalized isosteres of naphthalene derivatives.

| S-EPMC4216191 | biostudies-literature

Accessing 2-(hetero)arylmethyl-, -allyl-, and -propargyl-2,1-borazaronaphthalenes: palladium-catalyzed cross-couplings of 2-(chloromethyl)-2,1-borazaronaphthalenes.

Project description:The synthesis of 2-(chloromethyl)-2,1-borazaronaphthalene has provided an opportunity to expand dramatically the functionalization of the azaborines. This azaborinyl building block can serve as the electrophile in palladium-catalyzed cross-coupling reactions to form sp(3)-sp and sp(3)-sp(2) bonds. The cross-coupling reactions of 2-(chloromethyl)-2,1-borazaronaphthalene with potassium (hetero)aryl- and alkenyltrifluoroborates as well as terminal alkynes provides access to a variety of novel azaborines, allowing a library of pseudobenzylic substituted azaborines to be prepared from one common starting material.

| S-EPMC4251526 | biostudies-literature

Method for Accessing Nitrogen-Containing, B-Heteroaryl-Substituted 2,1-Borazaronaphthalenes.

Project description:The azaborine motif provides a mimic of aromatic systems through replacement of a C?C bond with a B-N bond. In particular, 2,1-borazaronaphthalenes, accessible through robust methods of synthesis and subsequent functionalization, afford an ideal platform to use for a variety of applications. However, the scope of substructures for this archetype has been limited by the lack of nitrogen-containing heteroaryls that can be incorporated within them. In this study, modified reaction conditions were developed to provide access to a wider range of substructures.

| S-EPMC5224235 | biostudies-literature

Accessing molecularly complex azaborines: palladium-catalyzed Suzuki-Miyaura cross-couplings of brominated 2,1-borazaronaphthalenes and potassium organotrifluoroborates.

Project description:Despite their potential applications in both medicinal chemistry and materials science, there have been limited reports on the functionalization of 2,1-borazaronaphthalenes since their discovery in 1959. To access new chemical space and build molecular complexity, the Suzuki-Miyaura cross-coupling of brominated 2,1-borazaronaphthalenes has been investigated. The palladium-catalyzed cross-coupling proceeds with an array of potassium (hetero)aryltrifluoroborates in high yield with low catalyst loadings under mild reaction conditions. By the use of a high-yielding bromination of various 2,1-borazaronaphthalenes to generate electrophilic azaborine species, a library of 3-(hetero)aryl and 3,6-diaryl-2,1-borazaronaphthalenes has been synthesized.

| S-EPMC4104828 | biostudies-other

Photoredox Catalysis Enables Access to N-Functionalized 2,1-Borazaronaphthalenes.

Project description:The synthesis and utilization of a class of 2,1-borazaronaphthyltrifluoroborate reagents that provide a general solution to the challenge of N-functionalization of the 2,1-borazaronaphthalene core is described. By adorning the nitrogen of this core with a trifluoroboratomethyl unit, a suite of odd-electron processes can be executed, installing motifs that would otherwise be inaccessible using a two-electron approach. In addition, this process enables rapid annulation, furnishing a heretofore unknown polycyclic B-N species.

| S-EPMC6490172 | biostudies-literature

Suzuki-Miyaura cross-coupling of brominated 2,1-borazaronaphthalenes with potassium alkenyltrifluoroborates.

Project description:Conditions have been developed for the palladium-catalyzed cross-coupling of 3-bromo-2,1-borazaronaphthalenes with potassium alkenyltrifluoroborates. Twenty-seven alkenyl-substituted azaborines have been synthesized through this method, providing access to a family of 2,1-borazaronaphthalenes with alkenyl substitution at the C3 position.

| S-EPMC4242045 | biostudies-literature

Regioselective Diversification of 2,1-Borazaronaphthalenes: Unlocking Isosteric Space via C-H Activation.

Project description:Methods for the regioselective C-H borylation and subsequent cross-coupling of the 2,1-borazaronaphthalene core are reported. Azaborines are dependent on B-N/C═C isosterism when employed in strategies for developing diverse heterocyclic scaffolds. Although 2,1-borazaronaphthalene is closely related to naphthalene in terms of structure, the argument is made that the former has electronic similarities to indole. Based on that premise, iridium-mediated C-H activation has enabled facile installation of a versatile, nucleophilic coupling handle at a previously inaccessible site of 2,1-borazaronaphthalenes. A variety of substituted 2,1-borazaronaphthalene cores can be successfully borylated and further cross-coupled in a facile manner to yield diverse C(8)-substituted 2,1-borazaronaphthalenes.

| S-EPMC5548096 | biostudies-literature

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

Project description: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.

| S-EPMC8156957 | biostudies-literature

A convergent, modular approach to functionalized 2,1-borazaronaphthalenes from 2-aminostyrenes and potassium organotrifluoroborates.

Project description:Azaborines are an important class of compounds with applications in both medicinal chemistry and materials science. The first borazaronaphthalene, 2-chloro-2,1-borazaronaphthalene, was reported in 1959; however, access to more highly functionalized substructures has been limited because of the harsh reaction conditions required to displace the chloride on boron. A convergent approach has been developed to synthesize disubstituted 2,1-borazaronaphthalenes from N-substituted 2-aminostyrenes and potassium organotrifluoroborates, where the potassium organotrifluoroborate is converted to the active R-BX2 species (X = Cl or F) in situ by addition of a fluorophile. Starting from aryl-, heteroaryl-, alkynyl-, alkenyl-, and alkyltrifluoroborates, a library of highly functionalized 2,1-borazaronaphthalenes were synthesized in one step under mild, transition-metal-free conditions.

| S-EPMC3932559 | biostudies-literature

Nickel-catalyzed alkyl-arylation of 3,3,3-trifluoropropene

Project description:Owing to the versatile synthetic utility of its carbon-carbon double bond, low-cost industrial chemical 3,3,3-trifluoropropene (TFP) represents one of the most straightforward and cost-efficient precursors to prepare trifluoromethylated compounds. However, only limited methods for the efficient transformations of TFP have been reported so far. Here, we report a nickel-catalyzed dicarbofunctionalization of TFP. The reaction uses inexpensive NiCl2·6H2O as the catalyst and 4,4’-biMeO-bpy and PCy2Ph as the ligands, allowing the alkyl-arylation of TFP with a variety of tertiary alkyl iodides and arylzinc reagents in high efficiency. This nickel-catalyzed process overcomes the previous challenges by suppressing β-H and β-F eliminations from TFP, rendering this strategy effective for the transformations of TFP into medicinal interest trifluoromethylated compounds. 3,3,3-Trifluoropropene is a cost-efficient precursor for the preparation of trifluoromethylated compounds, but limited methods for its efficient transformation have been reported. Here, nickel-catalyzed alkyl-arylation of 3,3,3-trifluoropropene with tertiary alkyl iodides and arylzinc reagents is achieved with high efficiency.

| S-EPMC9814099 | 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