Browse
Submit Data
Databases
API
Help

Dataset Information

12 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct synthesis and applications of solid silylzinc reagents.

ABSTRACT: The increased synthetic utility of organosilanes has motivated researchers to develop milder and more practical synthetic methods. Silylzinc reagents, which are typically the most functional group tolerant, are notoriously difficult to synthesize because they are obtained by a pyrophoric reaction of silyllithium, particularly Me₃SiLi which is itself prepared by the reaction of MeLi and disilane. Furthermore, the dissolved LiCl in silylzinc may have a detrimental effect. A synthetic method that can avoid silyllithium and involves a direct synthesis of silylzinc reagents from silyl halides is arguably the simplest and most economical strategy. We describe, for the first time, the direct synthesis of PhMe₂SiZnI and Me₃SiZnI reagents by employing a coordinating TMEDA ligand, as well as single crystal XRD structures. Importantly, they can be obtained as solids and stored for longer periods at 4 °C. We also demonstrate their significance in cross-coupling of various free alkyl/aryl/alkenyl carboxylic acids with broader functional group tolerance and API derivatives. The general applicability and efficiency of solid Me₃SiZnI are shown in a wide variety of reactions including alkylation, arylation, allylation, 1,4-addition, acylation and more.

SUBMITTER: Chandrasekaran R

PROVIDER: S-EPMC8654096 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Synthesis of solid 2-pyridylzinc reagents and their application in Negishi reactions.

Project description:In search of alternatives to unstable or unreliable 2-pyridylboron reagents, we have explored two new varieties of solid, moderately air-stable 2-pyridylzinc reagents. Both reagents can be manipulated in air and are competent nucleophiles in Negishi cross-coupling reactions.

| S-EPMC3869385 | biostudies-literature

Deprotection Reagents in Fmoc Solid Phase Peptide Synthesis: Moving Away from Piperidine?

Project description:The deprotection step is crucial in order to secure a good quality product in Fmoc solid phase peptide synthesis. 9-Fluorenylmethoxycarbonyl (Fmoc) removal is achieved by a two-step mechanism reaction favored by the use of cyclic secondary amines; however, the efficiency of the reaction could be affected by side reactions and by-product formation. Several aspects have to be taken into consideration when selecting a deprotection reagent: its physicochemical behavior, basicity (pKa) and polarity, concentration, and time of reaction, toxicity and disposability of residues and, finally, availability of reagents. This report presents a comparison of the performance of three strategies for deprotection using microwave-assisted Fmoc peptide synthesis. Four peptide sequences were synthesized using Rink amide resin with a Liberty Blue™ automated synthesizer and 4-methylpiperidine (4MP), piperidine (PP), and piperazine (PZ) as Fmoc removal reagents. In the first instance all three reagents behaved similarly. A detailed analysis showed a correlation between the hydrophobicity and size of the peptide with the yield and purity of the obtained product. The three reagents are interchangeable, and replacement of piperidine could be advantageous regarding toxicity and reagent handling.

| S-EPMC6274427 | biostudies-literature

Synthesis of nucleoside mono-, di-, and triphosphoramidates from solid-phase cyclosaligenyl phosphitylating reagents.

Project description:Chloromethyl polystyrene resin was reacted with 5-hydroxysalicylaldehyde in the presence of potassium carbonate to afford polymer-bound 2-hydroxybenzaldehyde. Subsequent reduction with borane solution produced polymer-bound 2-hydroxybenzyl alcohol. The reaction of immobilized 2-hydroxybenzyl alcohol with appropriate phosphitylating reagents yielded solid-phase cycloSaligenyl mono-, di-, and triphosphitylating reagents, which were reacted with unprotected nucleosides, followed by iodine oxidation, deprotection of cyanoethoxy groups, and the basic cleavage, respectively, to afford 5'-O-nucleoside mono-, di-, and triphosphoramidates in 52-73% overall yield.

| S-EPMC2688834 | biostudies-literature

Direct solid-phase synthesis of molecular heterooligonuclear lanthanoid-complexes.

Project description:Molecular lanthanoid complexes are highly valuable building blocks for a number of important technological applications, e.g. as contrast agents in magnetic resonance imaging (MRI) or as luminescent probes for bioassays. For the next generation of advanced applications based on molecular species, heterooligonuclear lanthanoid complexes with well-defined chemical and structural compositions are required. The great kinetic lability of trivalent lanthanoids so far prevents the realization of such molecular architectures with a universally applicable methodology. Here, we have developed functionalized molecular lanthanoid cryptates as monomeric building blocks which can be directly linked by standard solid-phase peptide synthesis to yield sequence-specific heterooligonuclear lanthanoid complexes. These molecular materials enable unique applications such as the generation of molecular codes with very convenient luminescence read-out.

| S-EPMC7067767 | biostudies-literature

Direct Fmoc-chemistry-based solid-phase synthesis of peptidyl thioesters.

Project description:Attachment of a growing peptide chain to a glycylaminomethyl resin via a thioglycinamide bond is compatible with Fmoc-chemistry solid-phase peptide synthesis. Subsequent S-alkylation of the thioamide gives a thioimide that, on treatment with aqueous trifluoroacetic acid, releases the peptide from the resin in the form of a C-terminal thioester.

| S-EPMC3184774 | biostudies-literature

Direct Analysis of Gene Synthesis Reactions Using Solid-State Nanopores.

Project description:Synthetic nucleic acids offer rich potential to understand and engineer new cellular functions, yet an unresolved limitation in their production and usage is deleterious products, which restrict design complexity and add cost. Herein, we employ a solid-state nanopore to differentiate molecules of a gene synthesis reaction into categories of correct and incorrect assemblies. This new method offers a solution that provides information on gene synthesis reactions in near-real time with higher complexity and lower costs. This advance can permit insights into gene synthesis reactions such as kinetics monitoring, real-time tuning, and optimization of factors that drive reaction-to-reaction variations as well as open venues between nanopore-sensing, synthetic biology, and DNA nanotechnology.

| S-EPMC5154552 | biostudies-literature

Convenient Synthesis of Benziodazolone: New Reagents for Direct Esterification of Alcohols and Amidation of Amines.

Project description:Hypervalent iodine heterocycles represent one of the important classes of hypervalent iodine reagents with many applications in organic synthesis. This paper reports a simple and convenient synthesis of benziodazolones by the reaction of readily available iodobenzamides with m-chloroperoxybenzoic acid in acetonitrile at room temperature. The structure of one of these new iodine heterocycles was confirmed by X-ray analysis. In combination with PPh3 and pyridine, these benziodazolones can smoothly react with alcohols or amines to produce the corresponding esters or amides of 3-chlorobenzoic acid, respectively. It was found that the novel benziodazolone reagent reacts more efficiently than the analogous benziodoxolone reagent in this esterification.

| S-EPMC8659036 | biostudies-literature

Synthesis of polymer-bound 4-acetoxy-3-phenylbenzaldehyde derivatives: applications in solid-phase organic synthesis.

Project description:Aminomethyl polystyrene resin was reacted with 4-(5'-formyl-2'-hydroxyphenyl)benzoic acid and 4-(5'-formyl-2'-hydroxyphenyl)phenyl propionic acid, respectively, in the presence of 1-hydroxybenzotriazole and 1,3-diisopropylcarbodiimide to yield polymer-bound benzaldehydes. The phenolic group in resins was acetylated with acetic anhydride to afford two polymer-bound 4-acetoxybenzaldehydes. The reductive amination of polymer-bound linkers by amines and sodium triacetoxyborohydride, followed by sulfonylation with arylsulfonyl chloride derivatives in the presence of pyridine and the cleavage with TFA/DCM/H2O, produced pure sulfonamides.

| S-EPMC2532670 | biostudies-literature

Yellow-Emitting Hydrophobic Carbon Dots via Solid-Phase Synthesis and Their Applications.

Project description:The preparation and application of hydrophobic carbon dots (HCDs) are now the hotspots in the field of nanomaterials. This paper reports the fast synthesis of long-wavelength-emitting HCDs (yellow-emitting, λem = 541 nm) through a solid-phase route, with l-cysteine hydrochloride anhydrous and citric acid as carbon sources and dicyclohexylcarbodiimide as a dehydrating agent, reacting at 180 °C for 40 min, with a quantum yield of 30%. The solid-phase route avoids the usage of organic reagents during the synthesis process and is thus environmentally friendly. The obtained HCDs can be simply separated into HCDs-L (less density) and HCDs-W (higher density) with differences in physical (polarity, density), optical, and chemical properties. The differences in HCDs-L, HCDs-W, and water-soluble CDs (WCDs) were compared through various characterization methods, and the synthesis and luminescence mechanisms of HCDs were investigated. Meanwhile, HCDs were employed in the fields of LED lamp production and solid fluorescent shaping material. The prepared HCDs were then modified into WCDs through the liposomal embedding method. The HCDs prepared by the new solid-phase route exhibit stable and highly efficient photoluminescence ability and will have a promising outlook in their applications in various fields.

| S-EPMC7482243 | biostudies-literature

Synthesis and Solid State Structure of Fluorous Probe Molecules for Fluorous Separation Applications.

Project description:A series of colored hydrocarbon and fluorocarbon tagged 1-fluoro-4-alkylamino-anthraquinones and 1,4-bis-alkylamino-anthraquinone probe molecules were synthesized from a (fluorinated) alkyl amine and 1,4-difluoroanthraquinone to aid in the development of fluorous separation applications. The anthraquinones displayed stacking of the anthraquinone tricycle and interdigitation of the (fluorinated) alkyl chains in the solid state. Furthermore, intramolecular N-H···O hydrogen bonds forced the hydrocarbon and fluorocarbon tags into a conformation pointing away from the anthraquinone tricycle, with the angle of the tricycle plane normal and the main (fluorinated) alkyl vector ranging from 1 to 39°. Separation of the probe molecules on fluorous silica gel showed that the degree of fluorination of the probe molecules plays only a minor role with most eluents (e.g., hexane-ethyl acetate and methyl nonafluorobutyl ethers-ethyl acetate). However, toluene as eluent caused a pronounced separation by degree of fluorination for fluorocarbon, but not hydrocarbon tagged probe molecules on both silica gel and fluorous silica gel. These studies suggest that hydrocarbon and fluorocarbon tagged anthraquinones are useful probe molecules for the development of laboratory scale fluorous separation applications.

| S-EPMC2840617 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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