Palladium Catalysed Reaction

Sclareol, a bioactive diterpene alcohol isolated from Salvia sclarea , was subjected to structural modification and cytotoxic evaluation. Boron-Heck-coupled analogs of manoyl oxide were prepared from sclareol in a two-step reaction scheme. In the first step manoyl oxide was prepared from sclareol using cerium (IV) ammonium nitrate. Further the structural modification of manoyl oxide via Palladium (II) catalysed Boron-Heck coupling reaction produced a new series of compounds. All the synthesised compounds were screened for in vitro cytotoxic evaluation against four cancer cell lines HCT-116, MCF-7, MDA-MB231and MDA-MB468...

Carbon isotope labelling of bioactive molecules is essential for accessing the pharmacokinetic and pharmacodynamic properties of new drug entities. Aryl carboxylic acids represent an important class of structural motifs ubiquitous in pharmaceutically active molecules and are ideal targets for the installation of a radioactive tag employing isotopically labelled CO2 . However, direct isotope incorporation via the reported catalytic reductive carboxylation (CRC) of aryl electrophiles relies on excess CO2 , which is incompatible with carbon-14 isotope incorporation...

Reaction conditions that are generally applicable to a wide variety of substrates are highly desired, especially in the pharmaceutical and chemical industries1-6 . Although many approaches are available to evaluate the general applicability of developed conditions, a universal approach to efficiently discover these conditions during optimizations is rare. Here we report the design, implementation and application of reinforcement learning bandit optimization models7-10 to identify generally applicable conditions by efficient condition sampling and evaluation of experimental feedback...

Using a straightforward sequence of diphosphonylation and a Pd-catalysed concerted-metalation-deprotonation (CMD), a synthetic strategy towards polyaromatic phosphorus containing rings was developed. Herein, we report the synthesis and characterization of new azaphosphaphenalenes, using easily accessible palladium catalysts and starting materials. The key tetrahydroquinoline intermediates of the reaction were synthesised via a fast and effective procedure and could be isolated as such, or further reacted towards the target polyaromatic structures...

Metal or metal cluster-doped zeolites catalyse a wide variety of reactions. In this work, a coupling reaction between bromobenzene and phenylboronic acid to yield biphenyl with the Pd-H-Beta zeolite catalyst was investigated with density functional theory (DFT) calculations. Utilizing a model system with tetrahedral Pd4 clusters within the H-Beta zeolite, it was demonstrated that the catalyst exhibited notable reactivity by effectively reducing the activation energy barrier for the reaction. Our investigation revealed that the zeolite framework facilitated electron transfer to the Pd cluster, thereby increasing the reaction activity...

Herein, we developed a palladium-catalysed C-H cyclisation of benzoic acids in chlorobenzene without additional oxidants. The key to the success of these reactions is the use of chlorobenzene, which serves a dual role as a solvent and an oxidant, thus providing a simple and efficient method for synthesising phthalides.

A series of novel diterpene-type 1,3-aminoalcohols and their regioisomers have been synthesised from natural stevioside in a stereoselective manner. The key intermediate β-keto alcohol was prepared using Wagner-Meerwein rearrangement of the epoxide derived from steviol methyl ester. The primary aminoalcohol was formed via Raney-nickel-catalysed hydrogenation of an oxime, and a versatile library of aminoalcohols was synthesised using a Schiff base with the primary amines. The aminoalcohol regioisomers were prepared from the mesylate of the β-keto alcohols...

Transformer-based large language models are making significant strides in various fields, such as natural language processing1-5 , biology6,7 , chemistry8-10 and computer programming11,12 . Here, we show the development and capabilities of Coscientist, an artificial intelligence system driven by GPT-4 that autonomously designs, plans and performs complex experiments by incorporating large language models empowered by tools such as internet and documentation search, code execution and experimental automation...

The aim of this project was to develop a synthetic protocol for the preparation of a cephamycin scaffold that would readily allow the synthesis of its analogues with variations at the C-7 amino group and the C-3' position. We also aimed to develop a method that avoided the use of toxic and potentially explosive diphenyldiazomethane. These aims were achieved via the synthesis of the novel α-bromo acetamide 18 which allowed functionalization at the α-bromo acetamide position by azide and then the introduction of a 4-phenyl-1 H -1,2,3-triazol-1-yl moiety via a Cu(I)-catalysed azide-alkyne cycloaddition reaction with phenylacetylene...

This report describes a one-pot multi-step procedure to obtain double azahelicenes via nucleophilic fluorine substitution of 2,2-di(2-bromophenyl)-1,1-difluoroalkenes and palladium-catalysed ring closing reaction. The developed synthesis approach allows easy diversification of substituents at all four fragments of the obtained X-shaped aza[4,6]helicene entity. Optical (UV/Vis, PL) and electrochemical (CV) properties of selected products were studied and experimental results are supported by (TD) DFT, NICS and NICS2BC calculations...

The Stille cross-coupling reaction is one of the most common strategies for the construction of C-C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium-catalysed Stille reactions, cost-effective nickel-catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped...

We have produced a novel indium-based metallocycle complex ( In-MeSH ), which we initially observed as an unanticipated side-product in metal-organic framework (MOF) syntheses. The serendipitously synthesized metallocycle forms via the acid-catalysed decomposition of dimethyl sulfoxide (DMSO) during solvothermal reactions in the presence of indium nitrate, dimethylformamide and nitric acid. A search through the Cambridge Structural Database revealed isostructural zinc, ruthenium and palladium metallocycle complexes formed by other routes...

Invited for this month's cover is the group of Evamarie Hey-Hawkins at Leipzig University. The cover picture shows the three different bonding modes (mono-, bi- and tridentate) of the modular ligand towards palladium(II) or platinum(II), illustrated with Winston who kindly served as the model. The cat has three binding sites (mouth, front paws and hind paws = P, N and pyridine) to bind the metal dichloride fragment. When all three are used in a tridentate bonding mode, one chlorido ligand is cleaved off. Cover design by Dr...

The Heck-Matsuda coupling reaction of arenediazonium salts derived from L-phenylalanine with various alkenes has been developed. A two-step process involving the preparation of a tetrafluoroborate diazonium salt from a 4-aminophenylalanine derivative, followed by a palladium(0)-catalysed Heck-Matsuda coupling reaction allowed access to a range of unnatural α-amino acids with cinnamate, vinylsulfone and stilbene side-chains. Analysis of the photophysical properties of these unnatural α-amino acids demonstrated that the ( E )-stilbene analogues exhibited fluorescent properties with red-shifted absorption and emission spectra and larger quantum yields than L-phenylalanine...

The design of highly active and structurally well-defined catalysts has become a crucial issue for heterogeneous catalysed reactions while reducing the amount of catalyst employed. Beside conventional synthetic routes, the employment of polynuclear transition metal complexes as catalysts or catalyst precursors has progressively intercepted a growing interest. These well-defined species promise to deliver catalytic systems where a strict control on the nuclearity allows to improve the catalytic performance while reducing the active phase loading...

Five new NNN pincer-type ligands and their palladium complexes were successfully synthesised and characterised by FT-IR, 1 H NMR, 13 C NMR, and UV-vis analyses. TEM analysis was used to observe the morphological character of the black residues obtained from the fourth cycle of the reusability test. Furthermore, suitable crystals of the N 2 , N 6 - bis (2- tert -butylphenyl)pyridine-2,6-dicarboxamide and its palladium complex were elucidated with the X-ray single crystal diffraction method. Both the ligand and its palladium complex crystallise in a monoclinic system with space group P 21 / c for the H2 L4 and C 2/ c for the palladium complex...

Regioselective B-H activation of o -carboranes is an effective way for constructing o -carborane derivatives, which have broad applications in medicine, catalysis and the wider chemical industry. However, the mechanistic basis for the observed selectivities remains unresolved. Herein, a series of density functional theory (DFT) calculations were employed to characterise the palladium N-heterocyclic carbene (Pd-NHC) catalysed regioselective B(3,6)-diarylation of o -carboranes. Computational results at the IDSCRF(ether)-LC-ωPBE/BS1 and IDSCRF(ether)-LC-ωPBE/BS2 levels showed that the reaction undergoes a Pd(0) → Pd(II) → Pd(0) oxidation/reduction cycle, with the regioselective B(3)-H activation being the rate-determining step (RDS) for the full reaction profile...

Triterpenoid natural products from the Schisandraceae family have long presented a significant synthetic challenge. Lancifodilactone I, a member of the family not previously synthesized, was identified as a key natural product target, from which many other members could be synthesized. We envisaged that the core ring system of lancifodilactone I could be accessed by a strategy involving palladium-catalysed cascade cyclisation of a bromoenynamide, via carbopalladation, Suzuki coupling and 8π-electrocyclisation, to synthesize the core 7,8-fused ring system...

Direct and selective functionalization of hydrocarbon chains is a fundamental problem in synthetic chemistry. Conventional functionalization of C=C double bonds and C(sp3 )-H bonds provides some solutions, but site diversity remains an issue. The merging of alkene isomerization with (oxidative) functionalization provides an ideal method for remote functionalization, which would provide more opportunities for site diversity. However, the reported functionalized sites are still limited and focus on a specific terminal position and internal site; new site-selective functionalization, including multi-functionalization, remains a largely unmet challenge...

An enantio- and diastereoselective Pd-catalysed (3 + 2) cycloaddition of bis(trifluoroethyl) 2-vinyl-cyclopropane-1,1-dicarboxylate (VCP) with cyclic sulfamidate imine-derived 1-azadienes (SDAs) has been developed. These reactions provide highly functionalized spiroheterocycles having three contiguous stereocentres, including a tetrasubstituted carbon bearing an oxygen functionality. The two geminal trifluoroethyl ester moieties can be manipulated in a facially selective manner to afford more diversely decorated spirocycles with four contiguous stereocentres...