Put a label on it: Carbon dioxide with H2 is shown to be an efficient and selective methylation reagent for aromatic aliphatic amines (see scheme; acac=acetylacetonate, triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane). A variety of functionalized including 13C-labelled drugs were obtained good yields functional-group tolerance. As service our authors readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed may re-organized online...

Benzylamines play a prominent role in numerous pharmaceutically active compounds. Thus, the development of novel, sustainable catalytic methodologies to provide access these privileged structural motifs is central importance. Herein we describe systematic study for construction large variety benzylamines using well-defined homogeneous iron complex. The methodology consists direct coupling readily available benzyl alcohols with simpler amines through borrowing hydrogen methodology, producing...

Formation of C-C bonds from CO2 is a much sought after reaction in organic synthesis. To date, other than C-H carboxylations using stoichiometric amounts metals, base, or organometallic reagents, little known about bond formation. In fact, to the best our knowledge no catalytic methylation and H2 has been reported. Described herein combination for efficient carbon nucleophiles such as indoles, pyrroles, electron-rich arenes. Comparison experiments which employ paraformaldehyde show similar...

We report herein the first catalytic strategy to harness amidyl radicals derived from N-chloroamides for C–C bond formation, allowing discovery of benzylic C–H difluoromethylation. Under copper-catalyzed conditions, a wide variety N-chlorocarboxamides and N-chlorocarbamates direct selective difluoromethylation with nucleophilic difluoromethyl source at room temperature. This scalable protocol exhibits broad substrate scope functional group tolerance, enabling late-stage bioactive molecules....

N-alkyl amino acids find widespread application as highly valuable, renewable building blocks. However, traditional synthesis methodologies to obtain these suffer from serious limitations, providing a major challenge develop sustainable alternatives. We report the first powerful catalytic strategy for direct N-alkylation of unprotected α-amino with alcohols. This method is selective, produces water only side product leading simple purification procedure, and variety are mono- or...

In Kombination mit H2 entpuppt sich Kohlendioxid als effizientes und selektives Methylierungsreagens für aromatische aliphatische Amine (siehe Schema; acac=Acetylacetonat, triphos=1,1,1-Tris(diphenylphosphanylmethyl)ethan). Eine Vielfalt funktionalisierter Amine, einschließlich 13C-markierter Wirkstoffe, wurde in guten Ausbeuten bei hoher Verträglichkeit funktionellen Gruppen erhalten.

[RuCl2(p-cymene)]2 in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be an extremely efficient catalyst for the cross-dehydrogenative C–H bond alkenylation reaction between benzoic acids alkenes. The could conducted at 80 °C using Cu(OAc)2·H2O as oxidant, yielding variety phthalide derivatives good excellent yields. More importantly, both Cu(OAc)2 PEG-400/H2O system easily recycled reused six times without any loss catalytic activity.

Pyrroles are prominent scaffolds in pharmaceutically active compounds and play an important role medicinal chemistry. Therefore, the development of new, atom-economic, sustainable catalytic strategies to obtain these moieties is highly desired. Direct pathways that utilize readily available alcohol substrates have been recently established; however, approaches rely on use noble metals such as ruthenium or iridium. Here, we report direct synthesis pyrroles using a catalyst based...

Abstract A novel class of chiral amphiphilic bifunctional thioureas based on a beyerane scaffold and each containing primary amino group were designed synthesized from the readily available natural product isosteviol. The shown to be effective for catalyzing asymmetric Michael additions between isobutyraldehyde nitroalkenes. thiourea 1a furnished S enantiomers, whereas 1b afforded R both with high yields (up 92 %) excellent enantioselectivities 98 %). Furthermore, reactions proceeded...

The use of a temporary protection by chloro group at C5 pyrazoles allows the synthesis 4-arylated pyrazoles, which were previously inaccessible palladium-catalyzed direct arylation, with complete regioselectivity and in high yields using most cases as little 0.5–0.1 mol % Pd(OAc)2 catalyst electron-deficient aryl bromides. Moreover, from 5-chloro-1,3-dimethylpyrazole, sequential catalytic C4 dechlorination, arylation reactions allowed 4,5-diarylated pyrazole derivative.

Abstract The influence of both electron‐withdrawing and electron‐donating substituents such as nitro, nitrile, chloro, bromo methoxy at C‐3 on fluorobenzenes for their palladium‐catalysed direct C‐2 arylation has been explored. With substituents, the reaction proceeds nicely using 2–4 mol% an air‐stable palladium complex potassium pivalate/dimethylacetamide (PivOK/DMA) catalytic system; in general, a very regioselective was observed. Moreover, variety aryl bromide coupling partner, benzoyl,...

Abstract Formation of CC bonds from CO 2 is a much sought after reaction in organic synthesis. To date, other than CH carboxylations using stoichiometric amounts metals, base, or organometallic reagents, little known about bond formation. In fact, to the best our knowledge no catalytic methylation and H has been reported. Described herein combination for efficient carbon nucleophiles such as indoles, pyrroles, electron‐rich arenes. Comparison experiments which employ paraformaldehyde show...

A recyclable K₂PtCl₄/Xphos-SO₃Na/PEG-400/H₂O system has been developed for highly regio- and stereoselective hydrosilylation of terminal alkynes leading exclusively to β-(<italic>E</italic>)-vinylsilanes.

The higher reactivity of C5-H bonds heteroarenes as compared to C-H bromopolyfluorobenzenes for palladium-catalyzed direct arylation allows the selective synthesis polyfluoroaryl-heteroarenes in moderate high yields, without bond functionalization polyfluorobenzene ring. In most cases, low loading Pd(OAc)2 catalyst (0.5-1 mol %) was employed. Then, from these heteroarylated polyfluorobenzenes, ring polyfluorobiphenyls.

To search for new environmentally benign insecticides with high activity, low toxicity, and residue, novel chiral configurations introduced into dicarboxamide scaffolds containing N-cyano sulfiliminyl moieties were first studied. Four series of phthalamides sulfur-containing side chains designed, synthesized, evaluated against oriental armyworm (Pseudaletia separata Walker) diamondback moth (Plutella xylostella (L.)) their insecticidal activities. All structures characterized by (1)H NMR,...

A highly efficient and practical method for the synthesis of<italic>N</italic>-arylsulfonamides has been developed by a heterogeneous copper-catalyzed Chan–Lam coupling between sulfonyl azides boronic acids.

Abstract In search of environmentally benign compounds with high biological activity, low toxicity and resistance, 8 novel benzoyl hydrazines containing pyrazole were designed synthesized. All characterized by 1 H NMR spectra HRMS. The preliminary results activity assessment indicated that most title exhibited certain insecticidal activities against Mythimna separata Walker at 200 mg·L −1 but excellent fungicidal six fungus 50 , which better than the control.

To tackle the serious challenge of insect resistance and stricter environmental regulations, innovating a new eco-friendly insecticide is urgently required. A series phthalamides containing sulfiliminyl sulfoximinyl moieties were designed synthesized. In total, 30 structures characterized by 1H NMR spectra HRMS. The bioassay results indicated that some title compounds exhibited excellent insecticidal activities against oriental armyworm (Pseudaletia separata Walker) diamondback moth...

The cross-dehydrogenative coupling of tertiary amines with nitroalkanes and ketones has been achieved using a recyclable magnetic nanoparticle-immobilized bipy–gold(<sc>iii</sc>) catalyst.

Abstract β-amino acid esters are important scaffolds in medicinal chemistry and valuable building blocks for materials synthesis. Surprisingly, the waste-free construction of such moieties from readily available or renewable starting has not yet been addressed. Here we report on a robust versatile method obtaining by direct amination β-hydroxyl via borrowing hydrogen methodology using cooperative catalytic system that comprises homogeneous ruthenium catalyst an appropriate Brønsted additive....

Abstract A modular and waste‐free strategy for constructing N ‐substituted cyclic amines via decarboxylative ‐alkylation of α‐amino acids employing ruthenium‐ iron‐based catalysts is presented. The reported method allows the synthesis a wide range five‐ six‐membered ‐alkylated heterocycles in moderate‐to‐excellent yields starting from predominantly proline broad benzyl alcohols, primary secondary aliphatic alcohols. Examples using pipecolic acid construction piperidine derivatives, as well...