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Use of Bromine and Bromo-Organic Compounds in Organic Synthesis

Bromination is one of the most important transformations in organic synthesis and can be carried out using bromine and many other bromo compounds. Use of molecular bromine in organic synthesis is well-known. However, due to the hazardous nature of bromine, enormous growth has been witnessed in the past several decades for the development of solid bromine carriers. This review outlines the use of bromine and different bromo-organic compounds in organic synthesis. The applications of bromine, a total of 107 bromo-organic compounds, 11 other brominating agents, and a few natural bromine sources were incorporated. The scope of these reagents for various organic transformations such as bromination, cohalogenation, oxidation, cyclization, ring-opening reactions, substitution, rearrangement, hydrolysis, catalysis, etc. has been described briefly to highlight important aspects of the bromo-organic compounds in organic synthesis.

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Direct regioselective phosphonation of heteroaryl N-oxides with H-phosphonates under metal and external oxidant free conditions

A direct C-H/P-H functionalization of heteroaryl N-oxides with H-phosphonates is described. A wide variety of heteroaryl phosphonates were obtained in up to 92% yield in a chemo- and regioselective manner, under oxidant and metal free conditions. This procedure features practicality, high efficiency, environmental friendliness and atom economy.

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C3-CARBON LINKED GLUTARIMIDE DEGRONIMERS FOR TARGET PROTEIN DEGRADATION

This invention provides Degronimers that have carbon-linked E3 Ubiquitin Ligase targeting moieties (Degrons), which can be linked to a targeting ligand for a protein that has been selected for in vivo degradation, and methods of use and compositions thereof as well as methods for their preparation.

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Catalyst-Controlled Selectivity in the Synthesis of C2- and C3-Sulfonate Esters from Quinoline N-Oxides and Aryl Sulfonyl Chlorides

The first example of the catalyst-controlled selective synthesis of C2- and C3-sulfonate-ester-substituted quinolines was developed by employing LaCl3 and chitosan@CuI catalysts, respectively. This protocol provides an expeditious route to an important class of quinoline derivatives frequently found in many biologically active compounds and features good practicality, high efficiency, and environmental friendliness. In addition, the easily recoverable chitosan@copper catalysts can be recycled five times without significant loss of catalytic performance.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Recent developments in the chemistry of heteroaromatic N -oxides

Selected developments in the chemistry of heteroaromatic N-oxides since 2001 are presented in this review. The use of these N-oxides, both in late-transition-metal-catalyzed oxidations of carbon-carbon triple bonds and in regioselective C-H functionalizations of the heteroarene, are contemporary topics of interest and the focus of the discussion. 1 Introduction 2 Synthesis of Heteroaromatic N-Oxides 2.1 Direct Oxidation of Hindered Heteroarenes 2.2 Through Construction of Heteroaromatic Rings 3 Heteroaromatic N-Oxides as Oxidants 3.1 Alkyne Oxidation 3.2 Allene Oxidation 3.3 Carbene Oxidation 4 Heteroaromatic N-Oxides as Substrates 4.1 Deoxygenative ortho-C-H Functionalization with Prior Activation 4.2 Deoxygenative ortho-C-H Functionalization with Nonstabilized Carbanions 4.3 Nondeoxygenative C-H Functionalization 4.3.1 ortho-C-H Functionalization 4.3.2 N-Oxide Directed ortho-Alkyl C-H Functionalization 4.3.3 N-Oxide Directed Remote C-H Functionalization 4.4 1,3-Dipolar Cycloaddition 5 Conclusion and Outlook.

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Mild and Efficient Deoxygenation of Amine-N-oxides with Titanium Tetrachloride-Indium System

TiCl4/In system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.

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Elimination of Carbon Monoxide by Electron Impact on Quinoline N-oxide, Carbostyril and 8-Hydroxyquinoline

Under electron impact, the molecular ions of quinoline N-oxide, carbostyril and 8-hydroxyquinoline lose carbon monoxide giving a fragment ion C8H7N (m/z 117), which was shown by collision-activated dissociation in each case to have the structure of the molecular ion of indole.Its formation from 8-hydroxyquinoline requires an unusual rearrangement.Isoquinoline N-oxide loses HCN rather than CO and gives a fragment which has the structure of the molecular ion of benzofuran.When the first three compounds were subjected to flash vacuum pyrolysis, quinoline N-oxide at 500-700 deg C gave carbostyril and indole was detected by gas chromatography/mass spectrometry.At 900 deg C carbostyril and 8-hydroxyquinoline both gave indole in small amounts, detected by gas chromatography/mass spectrometry.

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Synergy of anodic oxidation and cathodic reduction leads to electrochemical deoxygenative C2 arylation of quinoline: N-oxides

The first example of electrochemical deoxygenative C2 arylation of quinoline N-oxides using sulfonyl hydrazines was demonstrated in this work. By employing both anodic oxidation and cathodic reduction, a variety of 2-arylquinolines were synthesized under metal catalyst-, exogenous-oxidant-, and exogenous-reductant-free conditions.

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Synthesis of 1-(pyridyl, quinolyl, and isoquinolyl)azulenes by Reissert-Henze type reaction

Azulene derivatives reacted with N-oxide of several heterocycles in the presence of trifluoromethanesulfonic anhydride (Tf2O) to afford 1-(pyridyl, quinolyl, and isoquinolyl)azulenes in good yield, respectively. In the case of the reaction with the 1-azulenyl methyl sulfide (12), 1,1?-biazulene derivative 13 was obtained under the similar reaction conditions. The first synthesis of unsymmetrical 1,3-di(pyridyl)azulene derivative was also established via our new preparation method following the electrophilic pyridinylation using the reaction with pyridine in the presence of Tf2O.

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Nitrogen containing heterobicycles as factor Xa inhibitors

The present application describes nitrogen containing heterobicyclics and derivatives thereof, or pharmaceutically acceptable salt forms thereof, which are useful as inhibitors of factor Xa.

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