22069-99-4

Upstream product

• 583-53-9 2,3-dibromobenzene 
• 88-65-3 2-bromobenzoic-acid 
• 583-55-1 1-Bromo-2-iodobenzene 
• 73183-34-3 bis(pinacol)diborane 
• 615-36-1 2-bromoaniline 
• 19256-46-3 2-deuteriochlorobenzene 
• 2987-42-0 2-dideuterioaminobromobenzene 

Downstream Products

• 1232693-09-2 2-((2-deuterophenyl)diisopropylsilyl)pyridine 
• 1373945-02-8 2-(tert-butyl)-bis(2-deuteriophenyl)silyl-3-methoxyphenyl trifluoromethanesulfonate 
• 43019-96-1 d₂-benzoyl chloride 
• 1380546-52-0 2-deuterio-N-methoxybenzamide 
• 4551-39-7 2-deuteriobenzoic acid 
• 1447832-71-4 C₁₆H₁₅⁽²⁾H 
• 1431318-13-6 C₃₀H₂₃⁽²⁾H 
• 502925-48-6 (2-deuteriophenyl)boronic acid 
• 1015-89-0 6(5H)-phenanthridinone 

Relevant academic research and scientific papers

Investigations of the Alignment Process of PBPMLG: 2H NMR Analysis Reveals a Thermoresponsive 90° Flip of the Polymer

The application of anisotropic parameters in NMR-spectroscopy enables the acquisition of spatial and angular information, complementary to those from conventional isotropic NMR-measurements. The use of alignment media is a well-established method for inducing anisotropy. PBPMLG is a recently discovered polyglutamate-based alignment medium, exhibiting thermoresponsive behavior in the lyotropic liquid crystalline (LLC) phase, thus offering potential for deeper understanding of the alignment process. We present one approach for investigating the thermoresponsive behavior by synthesizing specifically deuterated PBPMLG-isotopologues and their subsequent analyses using 2H NMR-spectroscopy. It was possible to relate the observed thermoresponsive behavior to a flip of the polymer with respect to the external magnetic field—an effect never observed before in glutamate-based polymeric alignment media. Furthermore, a solvent-induced temperature dependent gelation was verified in THF, which might provide yet another opportunity to manipulate the properties of this alignment medium in the future.

Ni-Catalyzed Dual C-H Annulation of Benzimidazoles with Alkynes for Synthesis of π-Extended Heteroarenes

Transition metal catalyzed dual C-H activation and annulation with alkynes was an attractive protocol to construct polycyclic π-extended structures. However, most of them were dominated by noble metal catalysts. Disclosed herein was the study of base-metal Ni-catalysis for dual C-H annulation of N-aromatic imidazole, which produced a range of desired polycyclic aza-quinolines in 48-95% yields. The use of bifunctional phosphine oxide ligand proved to be critical for success.

Exploiting a silver-bismuth hybrid material as heterogeneous noble metal catalyst for decarboxylations and decarboxylative deuterations of carboxylic acids under batch and continuous flow conditions

Herein, we report novel catalytic methodologies for protodecarboxylations and decarboxylative deuterations of carboxylic acids utilizing a silver-containing hybrid material as a heterogeneous noble metal catalyst. After an initial batch method development, a chemically intensified continuous flow process was established in a simple packed-bed system which enabled gram-scale protodecarboxlyations without detectable structural degradation of the catalyst. The scope and applicability of the batch and flow processes were demonstrated through decarboxylations of a diverse set of aromatic carboxylic acids. Catalytic decarboxylative deuterations were achieved on the basis of the reaction conditions developed for the protodecarboxylations using D2O as a readily available deuterium source.

Co(III)-Catalyzed [4+1] Annulation of Amides with Allenes via C?H Activation

A Co(III)-catalyzed [4+1] annulation of amides with allenes to synthesize isoindolone and 1,5-dihydro-pyrrol-2-one derivatives is reported. A wide range of aromatic and vinylic amides react with allenes to give the corresponding annulation products in good to excellent yields. The mechanistic studies strongly support that the catalytic reaction proceeds through an amide-directed C?H activation, followed by carbocobaltation of allene, β-hydride elimination, and an intramolecular 1,2-hydroamination. (Figure presented.).

Oxidatively Induced C-H Activation at High Valent Nickel

This communication describes a series of oxidatively induced intramolecular arene C-H activation reactions of NiII model complexes to yield NiIV σ-aryl products. These reactions proceed within 10 min at room temperature, which repres

Synthesis of isoquinolones: Via Rh-catalyzed C-H activation of substituted benzamides using air as the sole oxidant in water

Most of the metal-catalyzed C-H activation/annulation reactions were carried out in organic solvents using expensive oxidants such as Cu(ii) and Ag(i) salts. Here, we reported a new approach for a highly regioselective synthesis of isoquinolones from N-alkyl benzamides and alkynes using an Rh(iii) catalyst and inexpensive oxygen as the sole oxidant in an aqueous medium. In the reaction, water gave the highest product yield among the solvents used. In addition, at the end of the reaction, the isoquinolone product directly precipitated out from the aqueous solution. The methodology can be applied to a gram scale synthesis. This Rh(iii)-catalyzed reaction shows interesting meta selectivity with the meta substituted benzamide and shows various regioselectivities with different substituted alkynes. Moreover, the methodology can be applied to the preparation of biologically active compounds having the isoquinolone core.

Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: Turnover-limiting reductive elimination versus π-complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes-substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Au-Catalyzed Biaryl Coupling to Generate 5- To 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes - substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to ?-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the ?-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Ruthenium-Catalyzed C-H Alkynylation of Aromatic Amides with Hypervalent Iodine-Alkyne Reagents

An efficient C-H activation method for the ortho alkynylation of aromatic N-methoxyamides with hypervalent iodine-alkyne reagent using a ruthenium catalyst is described. The reaction proceeds under mild reaction conditions with broad substrate scope. A possible catalytic cycle involving a ruthenium carboxylate assisted C-H bond cleavage is proposed from the preliminary mechanistic evidence.

Rhodium-Catalyzed Regioselective Synthesis of Isoindolium Salts from 2-Arylpyridines and Alkenes in Aqueous Medium under Oxygen

A highly regioselective synthesis of pyrido[2,1-a]isoindolium salts from 2-arylpyridines and two equivalents of electron-deficient alkenes catalyzed by rhodium is demonstrated. The reaction was carried out in aqueous medium at 110 °C using inexpensive oxygen as oxidant. Reverse aza-Michael addition of the isoindolium salt occurs when the salt was treated with base to give a β-disubstituted alkene product. A reaction mechanism involving an ortho C–H olefination of 2-arylpyridine by alkene, intramolecular aza-Michael addition, deprotonation at the β-carbon of the alkene fragment followed by another Michael addition to give the final product is proposed. (Figure presented.).