Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation.

ABSTRACT: Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\bithiophene cross-coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero-porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions.

SUBMITTER: Cowie TY

PROVIDER: S-EPMC4502767 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation.

Cowie Thomas Y TY Kennedy Lorna L Żurek Justyna M JM Paterson Martin J MJ Bebbington Magnus W P MW

European journal of organic chemistry 20150429 17

Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\bithiophene cross-coupling would indeed occur, and this was demonstrated ...[more]

PMID: 26213484

Similar Datasets

In silico rationalisation of selectivity and reactivity in Pd-catalysed C-H activation reactions.

Project description:A computational approach has been developed to automatically generate and analyse the structures of the intermediates of palladium-catalysed carbon-hydrogen (C-H) activation reactions as well as to predict the final products. Implemented as a high-performance computing cluster tool, it has been shown to correctly choose the mechanism and rationalise regioselectivity of chosen examples from open literature reports. The developed methodology is capable of predicting reactivity of various substrates by differentiation between two major mechanisms - proton abstraction and electrophilic aromatic substitution. An attempt has been made to predict new C-H activation reactions. This methodology can also be used for the automated reaction planning, as well as a starting point for microkinetic modelling.

| S-EPMC7323619 | biostudies-literature

Atypical McMurry cross-coupling reactions leading to a new series of potent antiproliferative compounds bearing the key [ferrocenyl-ene-phenol] motif.

Project description:In the course of the preparation of a series of ferrocenyl derivatives of diethylstilbestrol (DES), in which one of the 4-hydroxyphenyl moieties was replaced by a ferrocenyl group, the McMurry reaction of chloropropionylferrocene with a number of mono-aryl ketones unexpectedly yielded the hydroxylated ferrocenyl DES derivatives, 5a-c, in poor yields (10%-16%). These compounds showed high activity on the hormone-independent breast cancer cell line MDA-MB-231 with IC50 values ranging from 0.14 to 0.36 µM. Surprisingly, non-hydroxylated ferrocenyl DES, 4, showed only an IC50 value of 1.14 µM, illustrating the importance of the hydroxyethyl function in this promising new series. For comparison, McMurry reactions of the shorter chain analogue chloroacetylferrocene were carried out to see the difference in behaviour with mono-aryl ketones versus a diaryl ketone. The effect of changing the length of the alkyl chain adjacent to the phenolic substituent of the hydroxylated ferrocenyl DES was studied, a mechanistic rationale to account for the unexpected products is proposed, and the antiproliferative activities of all of these compounds on MDA-MB-231 cells lines were measured and compared. X-ray crystal structures of cross-coupled products and of pinacol-pinacolone rearrangements are reported.

| S-EPMC6271948 | biostudies-literature

Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity <i>via</i> cross-coupling reactions.

Project description:Conjugated macrocycles can exhibit concealed antiaromaticity; that is, despite not being antiaromatic, under specific circumstances, they can display properties typically observed in antiaromatic molecules due to their formal macrocyclic 4n π-electron system. Paracyclophanetetraene (PCT) and its derivatives are prime examples of macrocycles exhibiting this behaviour. In redox reactions and upon photoexcitation, they have been shown to behave like antiaromatic molecules (requiring type I and II concealed antiaromaticity, respectively), with such phenomena showing potential for use in battery electrode materials and other electronic applications. However, further exploration of PCTs has been hindered by the lack of halogenated molecular building blocks that would permit their integration into larger conjugated molecules by cross-coupling reactions. Here, we present two dibrominated PCTs, obtained as a mixture of regioisomers from a three-step synthesis, and demonstrate their functionalisation via Suzuki cross-coupling reactions. Optical, electrochemical, and theoretical studies reveal that aryl substituents can subtly tune the properties and behaviour of PCT, showing that this is a viable strategy in further exploring this promising class of materials.

| S-EPMC10243434 | biostudies-literature

Rationalisation and visualisation of non-bonded interactions

Project description: Not available

| S-EPMC3606268 | biostudies-literature

Concise Synthesis of Macrocycles by Multicomponent Reactions.

Project description:A short reaction pathway was devised to synthesize a library of artificial 18-27-membered macrocycles. The five-step reaction sequence involves ring opening of a cyclic anhydride with a diamine, esterification, coupling with an amino acid isocyanide, saponification, and, finally, macro-ring closure using an Ugi or, alternatively, a Passerini multicomponent reaction. Three out of the five steps allow for the versatile introduction of linker elements, side chains, and substituents with aromatic, heteroaromatic, and aliphatic character. The versatile pathway is described for 15 different target macrocycles on a mmol scale. Artificial macrocycles have recently become of great interest due to their potential to bind to difficult post-genomic targets.

| S-EPMC6706064 | biostudies-literature

About the selectivity and reactivity of active nickel electrodes in C-C coupling reactions.

Project description:Active anodes which are operating in highly stable protic media such as 1,1,1,3,3,3-hexafluoroisopropanol are rare. Nickel forms, within this unique solvent, a non-sacrificial active anode at constant current conditions, which is superior to the reported powerful molybdenum system. The reactivity for dehydrogenative coupling reactions of this novel active anode increases when the electrolyte is not stirred during electrolysis. Besides the aryl-aryl coupling, a dehydrogenative arylation reaction of benzylic nitriles was found while stirring the mixture providing quick access to synthetically useful building blocks.

| S-EPMC9052091 | biostudies-literature

Intramolecular anodic olefin coupling reactions: use of the reaction rate to control substrate/product selectivity.

Project description: Not available

| S-EPMC3997792 | biostudies-literature

Regioselective Crossed Aldol Reactions under Mild Conditions via Synergistic Gold-Iron Catalysis.

Project description:A synergistic gold/iron catalytic system was developed for sequential alkyne hydration and vinyl gold addition to aldehydes or ketones. Fe(acac)3 was identified as an essential co-catalyst in preventing vinyl gold protodeauration and facilitating nucleophilic additions. Effective C-C bond formation was achieved under mild conditions (r.t.) with excellent regioselectivity and high efficiency (1% [Au], up to 95% yields). Extending reaction scope to intramolecular fashion achieved successful macrocyclization (16-31 ring sizes) with excellent yields (up to 90%, gram-scale) without extended dilution (0.2 M), which highlighted the great potential of this new crossed-aldol strategy in challenging target molecule synthesis.

| S-EPMC10798669 | biostudies-literature

Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions.

Project description:A series of tetraamino-bisthiourea chiral macrocycles containing two diarylthiourea and two chiral diamine units were synthesized by a fragment-coupling approach in high yields. Different chiral diamine units, including cyclohexanediamines and diphenylethanediamines were readily incorporated by both homo and hetero [1 + 1] macrocyclic condensation of bisamine and bisisothiocyanate fragments. With the easy synthesis, gram-scale of macrocycle products can be readily obtained. These chiral macrocycles were applied in catalyzing bioinspired decarboxylative Mannich reactions. Only 5 mol % of the optimal macrocycle catalyst efficiently catalyzed the decarboxylative addition of a broad scope of malonic acid half thioesters to isatin-derived ketimines with excellent yields and good enantioselectivity. The rigid macrocyclic framework and the cooperation between the thiourea and tertiary amine sites were found to be crucial for achieving efficient activation and stereocontrol. As shown in control experiments, catalysis with the acyclic analogues having the same structural motifs were non-selective.

| S-EPMC9086498 | biostudies-literature

Synthetic fermentation of ?-peptide macrocycles by thiadiazole-forming ring-closing reactions.

Project description:Macrocyclic ?-peptides were efficiently prepared using a thiadiazole-forming cyclization reaction between an ?-ketoacid and a thiohydrazide. The linear ?-peptide precursors were assembled from isoxazolidine monomers by ?-ketoacid-hydroxylamine (KAHA) ligations with a bifunctional initiator - a process we have termed 'synthetic fermentation' due to the analogy of producing natural product-like molecules from simpler building blocks. The linear synthetic fermentation products underwent Boc-deprotection/thiadiazole-forming macrocyclization under aqueous, acidic conditions to provide the cyclic products in a one-pot process. This reaction sequence proceeds from easily accessed initiator and monomer building blocks without the need for additional catalysts or reagents, enabling facile production of macrocyclic ?-peptides, a relatively underexplored structural class.

| S-EPMC5896468 | 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