Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Orthogonal reactivity in boryl-substituted organotrifluoroborates.

ABSTRACT: A method was developed for the hydroboration of alkenyl-containing organotrifluoroborates to generate dibora intermediates. The reactivity differences between organotrifluoroborates and trialkylboranes facilitated the cross-coupling of the borane moiety of these intermediates in a highly chemoselective fashion with aryl halides, leaving the trifluoroborate intact for subsequent transformation. A one-pot hydroboration/two-directional cross-coupling sequence was also demonstrated, providing the fully elaborated products in good yields. These conditions were also amenable in the cross-coupling of trialkylboranes to halo-containing organotrifluoroborates. The stability of the trifluoroborate moiety to these conditions allows simple and efficient strategies for complex molecule construction.

SUBMITTER: Molander GA

PROVIDER: S-EPMC2645949 | biostudies-literature | 2008 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Orthogonal reactivity in boryl-substituted organotrifluoroborates.

Molander Gary A GA Sandrock Deidre L DL

Journal of the American Chemical Society 20081101 47

A method was developed for the hydroboration of alkenyl-containing organotrifluoroborates to generate dibora intermediates. The reactivity differences between organotrifluoroborates and trialkylboranes facilitated the cross-coupling of the borane moiety of these intermediates in a highly chemoselective fashion with aryl halides, leaving the trifluoroborate intact for subsequent transformation. A one-pot hydroboration/two-directional cross-coupling sequence was also demonstrated, providing the fu ...[more]

PMID: 18980313

Similar Datasets

Boryl (Hetero)aryne Precursors as Versatile Arylation Reagents: Synthesis through C-H Activation and Orthogonal Reactivity.

Project description:(Pinacolato)boryl ortho-silyl(hetero)aryl triflates are presented as a new class of building blocks for arylation. They demonstrate unique versatility by delivering boronate or (hetero)aryne reactivity chemoselectively in a broad range of transformations. This approach enables the unprecedented postfunctionalization of fluoride-activated (hetero)aryne precursors, for example, as substrates in transition-metal catalysis, and offers valuable new possibilities for aryl boronate postfunctionalization without the use of specialized protecting groups.

| S-EPMC4600243 | biostudies-literature

Oxidative condensations to form benzimidazole-substituted potassium organotrifluoroborates.

Project description:A library of benzimidazole-substituted potassium organotrifluoroborates was prepared via the condensation of various potassium formyl-substituted aryl- and heteroaryltrifluoroborates with aromatic 1,2-diamines under oxidative conditions. The efficient Suzuki-Miyaura cross-coupling of products thus formed to various aryl and heteroaryl bromides was achieved in good yields. The method allows the facile preparation of benzimidazole-containing triaromatic products in two steps from simple potassium formyl substituted aryl- or heteroaryltrifluoroborates.

| S-EPMC3428750 | biostudies-literature

Condensation reactions to form oxazoline-substituted potassium organotrifluoroborates.

Project description:A library of oxazoline-substituted potassium organotrifluoroborates was prepared via the condensation of various potassium formyl-substituted aryl- and heteroaryltrifluoroborates with tosylmethyl isocyanide under basic conditions. The efficient Suzuki-Miyaura cross-coupling of products thus formed to various aryl bromides was achieved in good yields. The method allows the facile preparation of oxazole-containing triaromatic products in two steps from simple potassium formyl-substituted aryl- or heteroaryltrifluoroborates.

| S-EPMC2749650 | biostudies-literature

Synthesis and reactivity of solid-supported organotrifluoroborates in Suzuki cross-coupling.

Project description:Solid-supported organotrifluoroborates were prepared in high yields by ion exchange with Amberlyst resins. The reactivity of solid supported aryltrifluoroborates was evaluated in Suzuki-Miyaura couplings with numerous aryl bromide partners. Electron-rich and -poor substituents were tolerated on both substrates, providing yields up to 90%. Examples of alkyl-, alkenyl-, alkynyl-, and heteroaryltrifluoborates were also successfully cross-coupled to aryl halides.

| S-EPMC3321116 | biostudies-literature

Isolation, structure and reactivity of a scandium boryl oxycarbene complex.

Project description:The reaction of a half-sandwich scandium boryl complex 1 with CO (1 atm) afforded a novel boryl oxycarbene complex 2. The structure of 2 was characterized by 1H, 13C and 11B NMR, X-ray diffraction, and DFT analysis. Further reaction of 2 with CO (1 atm) yielded a phenylamido- and boryl-substituted enediolate complex 3 through C-C bond formation between CO and the carbene unit in 2 and cleavage and rearrangement of the Si-N bond in the silylene-linked Cp-amido ligand. Upon heating, insertion of the carbene atom into a methine C-H bond in the boryl ligand of 2 took place to give an alkoxide complex 4. The reactions of 2 with pyridine and 2-methylpyridine led to insertion of the carbene atom into an ortho-C-H bond of pyridine and into a methyl C-H bond of 2-methylpyridine, respectively. The reaction of 2 with ethylene yielded a borylcyclopropyloxy complex 7 through cycloaddition of the carbene atom to ethylene.

| S-EPMC5580044 | biostudies-literature

Mapping the Electronic Structure and the Reactivity Trends for Stabilized α-Boryl Carbanions.

Project description:The chemistry of stabilized α-boryl carbanions shows remarkable diversity, and can enable many different synthetic routes towards efficient C-C bond formation. The electron-deficient, trivalent boron center stabilizes the carbanion facilitating its generation and tuning its reactivity. Here, the electronic structure and the reactivity trends of a large dataset of α-boryl carbanions are described. DFT-derived parameters were used to capture their electronic and steric properties, computational reactivity towards model substrates, and crystallographic analysis within the Cambridge Structural Dataset. This study maps the reactivity space by systematically varying the nature of the boryl moiety, the substituents of the carbanionic center, the number of α-boryl motifs, and the metal counterion. In general, the free carbanionic intermediates are described as borata-alkene species with C-B π interactions polarized towards the carbon. Furthermore, it was possible to classify the α-boryl alkylidene metal precursors into three classes directly related to their reactivity: 1) nucleophilic borata-alkene salts with alkali and alkaline earth metals, 2) nucleophilic η2 -(C-B) borata-alkene complexes with early transition metals, Cu and Ag, and 3) α-boryl alkyl complexes with late transition metals. This trend map aids selection of the appropriate reactive synthon depending on the reactivity sought.

| S-EPMC8457114 | biostudies-literature

Tuning SpyTag-SpyCatcher mutant pairs toward orthogonal reactivity encryption.

Project description:Genetically encoded covalent peptide tagging technology, such as the SpyTag-SpyCatcher reaction, has emerged as a unique way to do chemistry with proteins. Herein, we report the reactivity engineering of SpyTag-SpyCatcher mutant pairs and show that distinct reactivity can be encrypted for the same reaction based on protein sequences of high similarity. Valuable features, including high selectivity, inverse temperature dependence and (nearly) orthogonal reactivity, could be achieved based on as few as three mutations. This demonstrates the robustness of the SpyTag-SpyCatcher reaction and the plasticity of its sequence specificity, pointing to a family of engineered protein chemistry tools.

| S-EPMC5627348 | biostudies-literature

Quantitative and Orthogonal Formation and Reactivity of SuFEx Platforms.

Project description:The constraints of minute reactant amounts and the impossibility to remove any undesired surface-bound products during monolayer functionalization of a surface necessitate the selection of efficient, modular and orthogonal reactions that lead to quantitative conversions. Herein, we explore the character of sulfur-fluoride exchange (SuFEx) reactions on a surface, and explore the applicability for quantitative and orthogonal surface functionalization. To this end, we demonstrate the use of ethenesulfonyl fluoride (ESF) as an efficient SuFEx linker for creating "SuFEx-able" monolayer surfaces, enabling three distinct approaches to utilize SuFEx chemistry on a surface. The first approach relies on a di-SuFEx loading allowing dual functionalization with a nucleophile, while the two latter approaches focus on dual (CuAAC-SuFEx/SPOCQ-SuFEx) click platforms. The resultant strategies allow facile attachment of two different substrates sequentially on the same platform. Along the way we also demonstrate the Michael addition of ethenesulfonyl fluoride to be a quantitative surface-bound reaction, indicating significant promise in materials science for this reaction.

| S-EPMC6099289 | biostudies-literature

Expanded substrate scope and improved reactivity of ether-forming cross-coupling reactions of organotrifluoroborates and acetals.

Project description:Mixed acetals and organotrifluoroborates undergo BF(3)·OEt(2)-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF(3)·OEt(2)-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 °C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.

| S-EPMC3164939 | biostudies-literature

Palladium-Catalyzed Atroposelective Suzuki-Miyaura Coupling to Construct Axially Chiral Tetra-Substituted α-Boryl Styrenes.

Project description:Palladium-catalyzed Suzuki-Miyaura (SM) coupling is a valuable method for forming C─C bonds, including those between aryl moieties. However, achieving atroposelective synthesis of axially chiral styrenes via SM coupling remains challenging. In this study, a palladium-catalyzed atroposelective Suzuki-Miyaura coupling between gem-diborylalkenes and aryl halides is presented. Using the monophosphine ligand Me-BI-DIME (L2), a range of axially chiral tetra-substituted acyclic styrenes with high yields and excellent enantioselectivities are successfully synthesized. Control experiments reveal that the gem-diboryl group significantly influences the product enantioselectivities and the coupling prefers to occur at sites with lower steric hindrance. Additionally, the alkenyl boronate group in the products proves versatile, allowing for various transformations while maintaining high optical purities.

| S-EPMC11199998 | 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