117889-14-2

Upstream product

• 64-18-6 formic acid 
• 14268-66-7 benzo[1,3]dioxolo-5-ylamine 
• 2258-42-6 formyl acetic anhydride 
• 124-38-9 carbon dioxide 
• 2620-44-2 5-nitro-1,3-benzodioxole 
• 77287-34-4 formamide 
• 922-67-8 propynoic acid methyl ester 

Downstream Products

• 165459-70-1 3,4-(methylenedioxy)benzeneisonitrile 
• 1269206-04-3 [1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](4-chlorophenyl)methanone 
• 1268445-72-2 [1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](3-hydroxy-4-methoxyphenyl)methanone 
• 1268445-70-0 [1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](3,4,5-trimethoxyphenyl)methanone 
• 1269205-90-4 [1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](4-chlorophenyl)methanamine 
• 1268445-64-2 5-{amino[1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl]methyl}-2-methoxyphenol 
• 1268445-62-0 [1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](3,4,5-trimethoxyphenyl)methanamine 
• 1269205-83-5 1-[1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl]-N-benzyl-1-(4-chlorophenyl)methanamine 
• 1268445-53-9 5-{[1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl](benzylamino)methyl}-2-methoxyphenol 
• 1268445-51-7 1-[1-(benzo[d][1,3]dioxol-5-yl)-1H-tetrazol-5-yl]-N-benzyl-1-(3,4,5-trimethoxyphenyl)methanamine 
• 34060-22-5 N-methyl-3,4-(methylenedioxy)aniline 

Relevant academic research and scientific papers

Mild C?F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm

Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C?H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C?F bonds, one of the strongest σ-bonds, still remains challenging and new strategies for C?F activation are desirable. Herein a method for the photochemical activation of aromatic C?F bonds is presented. It is shown that isonitriles selectively insert into aromatic C?F bonds while aliphatic C?F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes. (Figure presented.).

Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide

We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.

Direct: N -formylation of nitroarenes with CO2

Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance of a wide range of nitroarenes and nitroheteroarenes.

Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines

A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.

Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins

A new strategy for constructing indolizino[1,2-b]quinolin-9(11H)-ones (ring cores of camptothecins) from readily available isocyanoarenes and N-(alkyl-2-yn-1-yl)pyridin-2(1H)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives.

Effective Synthesis of N-Arylformamide from α-Halo-N-arylacetamides

A convenient synthetic method for N-arylformamide derivatives was successfully developed by reacting α-iodo-N-arylacetamides with formamide. This method was applicable to α-iodo-N-arylacetamide substrates bearing electron-donating or electron-withdrawing groups, N-(benzo[d][1,3]dioxol-5-yl)-2-iodoacetamide, 2-iodo-N-(pyridin-2-yl)acetamide, and 2-iodo-N-(naphthalen-4-yl)acetamide to give the corresponding N-arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.

Radical perfluoroalkylation - Easy access to 2-perfluoroalkylindol-3-imines-via electron catalysis

Arylisonitriles (2 equivalents) react with alkyl and perfluoroalkyl radicals to form 2-alkylated indole-3-imines via two sequential additions to the isonitrile moiety followed by homolytic aromatic substitution. The three component reaction comprises three C-C bond formations. The endocyclic imine functionality in the products is more reactive in follow up chemistry and hydrolysis of the exocyclic imine leads to 3-oxindoles that show fluorescence properties.

Rhodium-catalyzed ortho C-H bond activation of arylamines for the synthesis of quinoline carboxylates

The rhodium catalyzed annulation of anilines with alkynic esters allowing for the high-yield synthesis of quinoline carboxylates with excellent regioselectivity is described. This unprecedented reaction employs either formic acid as the C1 source and reductant or copper(ii) as the oxidant and is proposed to proceed via rhodacycle of in situ generated amide and enamine ester followed by ortho C-H activation of arylamines with rhodium as the catalyst.

Transamidation of carboxamides catalyzed by Fe(III) and water

The highly efficient transamidation of several primary, secondary, and tertiary amides with aliphatic and aromatic amines (primary and secondary) is described. The reaction is performed in the presence of a 5 mol % concentration of different hydrated salts of Fe(III), and the results show that the presence of water is crucial. The methodology was also applied to urea and phthalimide to demonstrate its versatility and wide substrate scope. An example of its use is an intramolecular application in the synthesis of 2,3-dihydro-5H-benzo[b]-1,4- thiazepin-4-one, which is the bicyclic core of diltiazem and structurally related drugs (Budriesi, R.; Cosimelli, B.; Ioan, P.; Carosati, E.; Ugenti, M. P.; Spisani, R. Curr. Med. Chem. 2007, 14, 279-287). A plausible mechanism that explains the role of water is proposed on the basis of experimental observations and previous mechanistic suggestions for transamidation reactions catalyzed by transition metals such as copper and aluminum. This methodology represents a significant improvement over other existing methods; it can be performed in air and with wet or technical grade solvents.

PURINYL DERIVATIVES AND THEIR USE AS POTASSIUM CHANNEL MODULATORS

This invention relates to novel purinyl derivatives and their use as potassium channel modulating agents. Moreover the invention is directed to pharmaceutical compositions useful for the treatment or alleviation of diseases or disorders associated with the activity of potassium channels.