60787-31-7

Upstream product

• 2754-27-0 trimethylsilyl acetate 
• 38325-58-5 4-methoxyphenyl trimethylsilyl sulfide 
• 102-96-5 (2-nitroethenyl)benzene 
• 428442-20-0 3-[(4-methoxyphenyl)sulfanyl]-3-oxopropanoic acid 
• 33972-66-6 3-methyl-1-nitro-but-1-ene 
• 63668-66-6 S-(p-Methoxyphenyl)-3-oxobutanthioat 
• 696-63-9 4-Methoxybenzenethiol 
• 108-24-7 acetic anhydride 
• 6293-71-6 4,4'-dimethoxydiphenyliodonium iodide 
• 10387-40-3 potassium thioacetate 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 25753-16-6 4-(trifluoromethyl)benzoic anhydride 
• 75-36-5 acetyl chloride 
• 696-62-8 para-iodoanisole 

Downstream Products

• 14065-23-7 1-methoxy-2-[(4-methoxyphenyl)thio]benzene 
• 39141-48-5 Tri-(p-methoxythiophenyl)-orthoacetat-d⁽³⁾ 
• 1129-26-6 4-methoxybenzene sulfonamide 
• 5335-87-5 4,4'-dimethoxyphenyl disulfide 
• 623-12-1 4-chloromethoxybenzene 
• 98-68-0 4-methoxy-phenyl-sulphonyl chloride 

Relevant academic research and scientific papers

Synergistic Anion-(π)n-π Catalysis on π-Stacked Foldamers

In this report, we demonstrate that synergistic effects between π-π stacking and anion-π interactions in π-stacked foldamers provide access to unprecedented catalytic activity. To elaborate on anion-(π)n-π catalysis, we have designed, synthesized and evaluated a series of novel covalent oligomers with up to four face-to-face stacked naphthalenediimides (NDIs). NMR analysis including DOSY confirms folding into π stacks, cyclic voltammetry, steady-state and transient absorption spectroscopy the electronic communication within the π stacks. Catalytic activity, assessed by chemoselective catalysis of the intrinsically disfavored but biologically relevant addition reaction of malonate half thioesters to enolate acceptors, increases linearly with the length of the stacks to reach values that are otherwise beyond reach. This linear increase violates the sublinear power laws of oligomer chemistry. The comparison of catalytic activity with ratiometric changes in absorption and decreasing energy of the LUMO thus results in superlinearity, that is synergistic amplification of anion-π catalysis by remote control over the entire stack. In computational models, increasing length of the π-stacked foldamers correlates sublinearly with changes in surface potentials, chloride binding energies, and the distances between chloride and π surface and within the π stack. Computational evidence is presented that the selective acceleration of disfavored but relevant enolate chemistry by anion-π catalysis indeed originates from the discrimination of planar and bent tautomers with delocalized and localized charges, respectively, on π-acidic surfaces. Computed binding energies of keto and enol intermediates of the addition reaction as well as their difference increase with increasing length of the π stack and thus reflect experimental trends correctly. These results demonstrate that anion-(π)n-π interactions exist and matter, ready for use as a unique new tool in catalysis and beyond.

Anion-π Catalysts with Axial Chirality

The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis.

Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces

To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful. Served on a platter: Simple, compact, and precisely sculpted Leonard turns are introduced to firmly and reliably place reactions on aromatic surfaces, minimizing entropic costs to maximize enthalpic gains. The significant change in selectivity (ηd/f) from less desirable decarboxylation with loose turns (right) to more relevant enolate addition pathways on π-acidic surfaces with rigidified Leonard turns (left) demonstrates the power of this concept.

Electric-Field-Assisted Anion-π Catalysis

This report focuses on the remote control of anion-π catalysis by electric fields. We have synthesized and immobilized anion-π catalysts to explore the addition reaction of malonic acid half thioesters to enolate acceptors on conductive indium tin oxide surfaces. Exposed to increasing electric fields, anion-π catalysts show an increase in activity and an inversion of selectivity. These changes originate from a more than 100-fold rate enhancement of the disfavored enolate addition reaction that coincides with an increase in selectivity of transition-state recognition by up to -14.8 kJ mol-1. The addition of nitrate with strong π affinity nullified (IC50 = 2.2 mM) the responsiveness of anion-π catalysts to electric fields. These results support that the polarization of the π-acidic naphthalenediimide surface in anion-π catalysts with electric fields increases the recognition of anionic intermediates and transition states on this polarized π surface, that is, the existence and relevance of electric-field-assisted anion-π catalysis.

Anion–π Catalysis on Carbon Nanotubes

Induced π acidity from polarizability is emerging as the most effective way to stabilize anionic transition states on aromatic π surfaces, that is, anion–π catalysis. To access extreme polarizability, we propose a shift from homogeneous toward heterogeneo

Remote Control of Anion–π Catalysis on Fullerene-Centered Catalytic Triads

The design, synthesis and evaluation of catalytic triads composed of a central C60 fullerene with an amine base on one side and polarizability enhancers on the other side are reported. According to an enolate addition benchmark reaction, fullerene–fullerene–amine triads display the highest selectivity in anion–π catalysis observed so far, whereas NDI–fullerene–amine triads are not much better than fullerene–amine controls (NDI=naphthalenediimide). These large differences in activity are in conflict with the small differences in intrinsic π acidity, that is, LUMO energy levels and π holes on the central fullerene. However, they are in agreement with the high polarizability of fullerene–fullerene–amine triads. Activation and deactivation of the fullerene-centered triads by intercalators and computational data on anion binding further indicate that for functional relevance, intrinsic π acidity is less important than induced π acidity, that is, the size of the oriented macrodipole of polarizable π systems that emerges only in response to the interaction with anions and anionic transition states. The resulting transformation is thus self-induced, the anionic intermediates and transition states create their own anion–π catalyst.

Noncross-linked polystyrene nanoencapsulation of ferric chloride: A novel and reusable heterogeneous macromolecular Lewis acid catalyst toward selective acetylation of alcohols, phenols, amines, and thiols

Ferric chloride has been successfully nanoencapsulated for the first time on a non-cross-linked polystyrene matrix as the shell material via the coacervation technique. The resulting polystyrene nanoencapsulated ferric chloride was used as a novel and rec

Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst

Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.

NiNP@rGO Nanocomposites as Heterogeneous Catalysts for Thiocarboxylation Cross-Coupling Reactions

A new type of ligand-free Ni-nanoparticles supported on rGO (size distribution average d = 9 ± 3 nm) was prepared and fully characterized via morphological (Fe-SEM), structural (P-XRD, HR-TEM), and spectroscopic (ICP-EOS, XPS) analysis tools. The metal composite was effectively employed in the unprecedented heterogeneously Ni-assisted cross-coupling reaction of aryl/vinyl iodides and thiocarboxylates. A range of sulfur-containing aryl as well as vinyl derivatives (15 examples) was achieved in high yields (up to 82%), under mild reaction conditions, and with wide functional group tolerance.

Rhodium-catalyzed carbonylative coupling of alkyl halides with thiols: a radical process faster than easier nucleophilic substitution

How to make a carbonylative coupling faster than the easier nucleophilic substitution? In this communication, a rhodium-catalyzed radical-based carbonylative coupling of alkyl halides with thiolphenols has been realized. Thioesters were isolated in good y