Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Additive- and Metal-Free, Predictably 1,2- and 1,3-Regioselective, Photoinduced Dual C-H/C-X Borylation of Haloarenes.

ABSTRACT: We report herein a simple, additive- and metal-free, photoinduced, dual C-H/C-X borylation of chloro-, bromo-, and iodoarenes. The reaction produces 1,2- and 1,3-diborylarenes on gram scales under batch and continuous flow conditions. The regioselectivity of the dual C-H/C-X borylation is determined by the solvent and the substituents in the parent haloarenes.

SUBMITTER: Mfuh AM

PROVIDER: S-EPMC4958914 | biostudies-literature | 2016 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Additive- and Metal-Free, Predictably 1,2- and 1,3-Regioselective, Photoinduced Dual C-H/C-X Borylation of Haloarenes.

Mfuh Adelphe M AM Nguyen Vu T VT Chhetri Bhuwan B Burch Jessica E JE Doyle John D JD Nesterov Vladimir N VN Arman Hadi D HD Larionov Oleg V OV

Journal of the American Chemical Society 20160701 27

We report herein a simple, additive- and metal-free, photoinduced, dual C-H/C-X borylation of chloro-, bromo-, and iodoarenes. The reaction produces 1,2- and 1,3-diborylarenes on gram scales under batch and continuous flow conditions. The regioselectivity of the dual C-H/C-X borylation is determined by the solvent and the substituents in the parent haloarenes. ...[more]

PMID: 27347688

Similar Datasets

Metal- and additive-free photoinduced borylation of haloarenes.

Project description:Boronic acids and esters have critical roles in the areas of synthetic organic chemistry, molecular sensors, materials science, drug discovery, and catalysis. Many of the current applications of boronic acids and esters require materials with very low levels of transition metal contamination. Most of the current methods for the synthesis of boronic acids, however, require transition metal catalysts and ligands that must be removed via additional purification procedures. This protocol describes a simple, metal- and additive-free method of conversion of haloarenes directly to boronic acids and esters. This photoinduced borylation protocol does not require expensive and toxic metal catalysts or ligands, and it produces innocuous and easy-to-remove by-products. Furthermore, the reaction can be carried out on multigram scales in common-grade solvents without the need for reaction mixtures to be deoxygenated. The setup and purification steps are typically accomplished within 1-3 h. The reactions can be run overnight, and the protocol can be completed within 13-16 h. Two representative procedures that are described in this protocol provide details for preparation of a boronic acid (3-cyanopheylboronic acid) and a boronic ester (1,4-benzenediboronic acid bis(pinacol)ester). We also discuss additional details of the method that will be helpful in the application of the protocol to other haloarene substrates.

| S-EPMC5737794 | biostudies-literature

Scalable, Metal- and Additive-Free, Photoinduced Borylation of Haloarenes and Quaternary Arylammonium Salts.

Project description:We report herein a simple, metal- and additive-free, photoinduced borylation of haloarenes, including electron-rich fluoroarenes, as well as arylammonium salts directly to boronic acids. This borylation method has a broad scope and functional group tolerance. We show that it can be further extended to boronic esters and carried out on gram scale as well as under flow conditions.

| S-EPMC4974080 | biostudies-literature

Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes.

Project description:A highly enantioselective Cu-catalyzed borylation of 2-substituted 1,3-dienes is reported. The use of a chiral phosphanamine ligand is essential in achieving high chemo-, regio-, diastereo- and enantioselectivity. It provides access to a variety of homoallylic boronates in consistently high yield and enantiomeric excess with 2-aryl and 2-heteroaryl 1,3-dienes as well as sterically demanding 2-alkyl 1,3-dienes. Preliminary investigations based on a non-linear effect study point to a mechanism involving more than one metal center.

| S-EPMC6001400 | biostudies-literature

Metal-free, photoinduced remote C(sp<sup>3</sup>)-H borylation.

Project description:Here, we describe a protocol for the metal-free, photo-induced borylation of unactivated C(sp3)-H bonds distal to an O-oxalate hydroxamic ester functionality. The methodology requires only substrate and bis(catecholato)diboron under light irradiation to effect the desired transformation. A range of linear and cyclic tertiary and secondary borylation products are obtained in good yields and high site-selectivity enabling the late-stage C(sp3)-H borylation of natural product derivatives and drug-like compounds.

| S-EPMC10498503 | biostudies-literature

Additive-assisted regioselective 1,3-dipolar cycloaddition of azomethine ylides with benzylideneacetone.

Project description:1,3-Dipolar cycloadditions of isatins, benzylamine and benzylideneacetones were studied to prepare a series of novel spiropyrrolidine-oxindoles - 4'-acetyl-3',5'-diarylspiro[indoline-3,2'-pyrrolidin]-2-ones and 3'-acetyl-4',5'-diarylspiro[indoline-3,2'-pyrrolidine]-2-ones in good yields of up to 94% and with good regioselectivities. Regioselectivities are reversible by the addition of water or 4-nitrobenzoic acid, respectively. The substituent effects on the regioselectivity were also investigated.

| S-EPMC3943969 | biostudies-literature

Photoinduced metal-free borylation of aryl halides catalysed by an <i>in situ</i> formed donor-acceptor complex.

Project description:Organoboron compounds are very important building blocks which can be applied in medicinal, biological and industrial fields. However, direct borylation in a metal free manner has been very rarely reported. Herein, we described the successful direct borylation of haloarenes under mild, operationally simple, catalyst-free conditions, promoted by irradiation with visible light. Mechanistic experiments and computational investigations indicate the formation of an excited donor-acceptor complex with a -3.12 V reduction potential, which is a highly active reductant and can facilitate single-electron-transfer (SET) with aryl halides to produce aryl radical intermediates. A two-step one-pot method was developed for site selective aromatic C-H bond borylation. The protocol's good functional group tolerance enables the functionalization of a variety of biologically relevant compounds, representing a new application of aryl radicals merged with photochemistry.

| S-EPMC9067585 | biostudies-literature

Regioselective Arylboration of 1,3-Butadiene.

Project description:A method for the regioselective 1,2-arylboration of 1,3-butadiene, a feedstock chemical, is reported. The reactions result in the formation of products that can be easily elaborated to other structures. The mechanistic details of this process are also discussed.

| S-EPMC8046179 | biostudies-literature

Iridium-catalysed regioselective borylation of carboranes via direct B-H activation.

Project description:Carboranes are carbon-boron molecular clusters, which can be viewed as three-dimensional analogues to benzene. They are finding many applications in medicine, materials and organometallic chemistry. On the other hand, their exceptional thermal and chemical stabilities, as well as 3D structures, make them very difficult to be functionalized, in particular the regioselective functionalization of BH vertex among ten similar B-H bonds. Here we report a very efficient iridium-catalysed borylation of cage B(3,6)-H bonds of o-carboranes with excellent yields and regioselectivity using bis(pinacolato)diboron (B2pin2) as a reagent. Selective cage B(4)-H borylation has also been achieved by introducing a bulky TBDMS (tert-butyldimethylsilyl) group to one cage carbon vertex. The resultant 3,6-(Bpin)2-o-carboranes are useful synthons for the synthesis of a wide variety of B(3,6)-difunctionalized o-carboranes bearing cage B-X (X=O, N, C, I and Br) bonds.

| S-EPMC5357313 | biostudies-literature

Regioselective and Diastereoselective Aminoarylation of 1,3-Dienes.

Project description:The 1,4-functionalization of dienes is a synthetically useful strategy for incorporating molecular complexity into a class of simple substrates. We report the aminoarylation of acyclic and cyclic 1,3-dienes via the sequential [4+2] cycloaddition with a sulfurdiimide reagent and copper-catalyzed allylic substitution with Grignard reagents. The regioselective and diastereoselective aminoarylation of unsymmetrical dienes is also presented, which highlights the utility of this method for generating products with multiple functional groups and stereocenters.

| S-EPMC4242432 | biostudies-literature

One-Metal/Two-Ligand for Dual Activation Tandem Catalysis: Photoinduced Cu-Catalyzed Anti-hydroboration of Alkynes.

Project description:A dual catalyst system based on ligand exchange of two diphosphine ligands possessing different properties in a copper complex has been devised to merge metal- and photocatalytic activation modes. This strategy has been applied to the formal anti-hydroboration of activated internal alkynes via a tandem sequence in which Cu/Xantphos catalyzes the B2pin2-syn-hydroboration of the alkyne whereas Cu/BINAP serves as a photocatalyst for visible light-mediated isomerization of the resulting alkenyl boronic ester. Photochemical studies by means of UV-vis absorption, steady-state and time-resolved fluorescence, and transient absorption spectroscopy have allowed characterizing the photoactive Cu/BINAP species in the isomerization reaction and its interaction with the intermediate syn-alkenyl boronic ester through energy transfer from the triplet excited state of the copper catalyst. In addition, mechanistic studies shed light into catalyst speciation and the interplay between the two catalytic cycles as critical success factors.

| S-EPMC9348838 | 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