Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper(II)-Mediated [11C]Cyanation of Arylboronic Acids and Arylstannanes.

ABSTRACT: A copper-mediated method for the transformation of diverse arylboron compounds and arylstannanes to aryl-[11C]-nitriles is reported. This method is operationally simple, uses commercially available reagents, and is compatible with a wide variety of substituted aryl- and heteroaryl substrates. This method is applied to the automated synthesis of high specific activity [11C]perampanel in 10% nondecay-corrected radiochemical yield (RCY).

SUBMITTER: Makaravage KJ

PROVIDER: S-EPMC5892454 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper(II)-Mediated [11C]Cyanation of Arylboronic Acids and Arylstannanes.

Makaravage Katarina J KJ Shao Xia X Brooks Allen F AF Yang Lingyun L Sanford Melanie S MS Scott Peter J H PJH

Organic letters 20180227 6

A copper-mediated method for the transformation of diverse arylboron compounds and arylstannanes to aryl-[11C]-nitriles is reported. This method is operationally simple, uses commercially available reagents, and is compatible with a wide variety of substituted aryl- and heteroaryl substrates. This method is applied to the automated synthesis of high specific activity [11C]perampanel in 10% nondecay-corrected radiochemical yield (RCY). ...[more]

PMID: 29484880

Similar Datasets

Copper(I)-Mediated 11C-Carboxylation of (Hetero)arylstannanes.

Project description:A novel copper-mediated carboxylation strategy of aryl- and heteroaryl-stannanes is described. The method serves as a mild (i.e., 1 atm) carboxylation method using stable carbon dioxide and is transferable as a radiosynthetic approach for carbon-11-labeled aromatic and heteroaromatic carboxylic acids using sub-stoichiometric quantities of [11C]CO2. The methodology was applied to the radiosynthesis of the retinoid X receptor agonist, [11C]bexarotene, with a decay-corrected radiochemical yield of 32 ± 5% and molar activity of 38 ± 23 GBq/?mol (n = 3).

| S-EPMC7161067 | biostudies-literature

[11C]Cyanation of arylboronic acids in aqueous solutions.

Project description:A copper-mediated 11C-cyanation method employing arylboronic acids and [11C]HCN has been developed. This method was applied to the radiochemical synthesis of a wide range of aromatic 11C-nitriles in aqueous solutions. The use of readily accessible arylboronic acids as precursors makes this method complementary to the well-established 11C-cyanation methods that utilize aryl halide precursors.

| S-EPMC5584069 | biostudies-literature

Fast and efficient copper-mediated 18F-fluorination of arylstannanes, aryl boronic acids, and aryl boronic esters without azeotropic drying.

Project description:BackgroundCopper-mediated radiofluorination is a straightforward method to produce a variety of [18F]fluoroarenes and [18F]fluoroheteroarenes. To minimize the number of steps in the production of 18F-labelled radiopharmaceuticals, we have developed a short and efficient azeotropic drying-free 18F-labelling method using copper-mediated fluorination. Our goal was to improve the copper-mediated method to achieve wide substrate scope with good radiochemical yields with short synthesis time.ResultsSolid phase extraction with Cu (OTf)2 in dimethylacetamide is a suitable activation method for [18F]fluoride. Elution efficiency with Cu (OTf)2 is up to 79% and radiochemical yield (RCY) of a variety of model molecules in the crude reaction mixture has reached over 90%. Clinically relevant molecules, norepinephrine transporter tracer [18F]NS12137 and monoamine transporter tracer [18F]CFT were produced with 16.5% RCY in 98?min and 5.3% RCY in 64?min, respectively.ConclusionsCu (OTf)2 is a suitable elution agent for releasing [18F]fluoride from an anion exchange cartridge. The method is fast and efficient and the Cu-complex is customizable after the release of [18F]fluoride. Alterations in the [18F]fluoride elution techniques did not have a negative effect on the subsequent labelling reactions. We anticipate this improved [18F]fluoride elution technique to supplant the traditional azeotropic drying of [18F]fluoride in the long run and to concurrently enable the variations of the copper-complex.

| S-EPMC6795642 | biostudies-literature

Copper-mediated arylation with arylboronic acids: Facile and modular synthesis of triarylmethanes.

Project description:A facile and modular synthesis of triarylmethanes was achieved in good yield via a two-step sequence in which the final step is the copper(II)-catalyzed arylation of diarylmethanols with arylboronic acids. By using this protocol a variety of symmetrical and unsymmetrical triarylmethanes were synthesized. As an application of the newly developed methodology, we demonstrate a high-yielding synthesis of the triarylmethane intermediate towards an anti-breast-cancer drug candidate.

| S-EPMC4902010 | biostudies-literature

Copper-assisted palladium(II)-catalyzed direct arylation of cyclic enaminones with arylboronic acids.

Project description:Described herein is a palladium(II)-catalyzed direct arylation of cyclic enaminones with arylboronic acids. The versatility of this method is that both electron-rich and electron-poor boronic acids can be coupled in high yields. A mixture of two Cu(II) additives was crucial for efficient cross-coupling. The role of each Cu(II) reagent appears to be distinct and complementary serving to assist catalyst reoxidation and transmetalation through a putative arylcopper intermediate.

| S-EPMC3490213 | biostudies-literature

Copper-Mediated Radiofluorination of Arylstannanes with [18F]KF.

Project description:A copper-mediated nucleophilic radiofluorination of aryl- and vinylstannanes with [18F]KF is described. This method is fast, uses commercially available reagents, and is compatible with both electron-rich and electron-deficient arene substrates. This method has been applied to the manual synthesis of a variety of clinically relevant radiotracers including protected [18F]F-phenylalanine and [18F]F-DOPA. In addition, an automated synthesis of [18F]MPPF is demonstrated that delivers a clinically validated dose of 200 ± 20 mCi with a high specific activity of 2400 ± 900 Ci/mmol.

| S-EPMC5078836 | biostudies-literature

Palladium-catalyzed, copper(I)-mediated coupling of boronic acids and benzylthiocyanate. A cyanide-free cyanation of boronic acids.

Project description:A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields.

| S-EPMC2561219 | biostudies-literature

A Design of Experiments (DoE) Approach Accelerates the Optimization of Copper-Mediated 18F-Fluorination Reactions of Arylstannanes.

Project description:Recent advancements in 18F radiochemistry, such as the advent of copper-mediated radiofluorination (CMRF) chemistry, have provided unprecedented access to novel chemically diverse PET probes; however, these multicomponent reactions have come with a new set of complex optimization problems. Design of experiments (DoE) is a statistical approach to process optimization that is used across a variety of industries. It possesses a number of advantages over the traditionally employed "one variable at a time" (OVAT) approach, such as increased experimental efficiency as well as an ability to resolve factor interactions and provide detailed maps of a process's behavior. Here we demonstrate the utility of DoE to the development and optimization of new radiochemical methodologies and novel PET tracer synthesis. Using DoE to construct experimentally efficient factor screening and optimization studies, we were able to identify critical factors and model their behavior with more than two-fold greater experimental efficiency than the traditional OVAT approach. Additionally, the use of DoE allowed us to glean new insights into the behavior of the CMRF of a number of arylstannane precursors. This information has guided our decision-making efforts while developing efficient reaction conditions that suit the unique process requirements of 18F PET tracer synthesis.

| S-EPMC6684620 | biostudies-literature

C(sp3)-H cyanation by a formal copper(iii) cyanide complex.

Project description:High-valent metal oxo complexes are prototypical intermediates for the activation and hydroxylation of alkyl C-H bonds. Substituting the oxo ligand with other functional groups offers the opportunity for additional C-H functionalization beyond C-O bond formation. However, few species aside from metal oxo complexes have been reported to both activate and functionalize alkyl C-H bonds. We herein report the first example of an isolated copper(iii) cyanide complex (LCuIIICN) and its C-H cyanation reactivity. We found that the redox potential (E ox) of substrates, instead of C-H bond dissociation energy, is a key determinant of the rate of PCET, suggesting an oxidative asynchronous CPET or ETPT mechanism. Among substrates with the same BDEs, those with low redox potentials transfer H atoms up to a million-fold faster. Capitalizing on this mechanistic insight, we found that LCuIIICN is highly selective for cyanation of amines, which is predisposed to oxidative asynchronous or stepwise transfer of H+/e-. Our study demonstrates that the asynchronous effect of PCET is an appealing tool for controlling the selectivity of C-H functionalization.

| S-EPMC9891353 | biostudies-literature

Silver-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids.

Project description:A silver-mediated cross-coupling of trifluoromethoxide with aryl stannanes and arylboronic acids to give aryl trifluoromethyl ethers is reported. This is the first report of a transition-metal-mediated C(aryl)-OCF(3) bond formation.

| S-EPMC3218431 | biostudies-literature