Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper-catalyzed direct transformation of simple alkynes to alkenyl nitriles via aerobic oxidative N-incorporation.

ABSTRACT: A novel direct transformation of aliphatic terminal alkynes to alkenyl nitriles through the incorporation of a nitrogen atom into the simple hydrocarbons has been reported. The usage of inexpensive copper catalyst, O₂ as the sole oxidant, broad substrate scope as well as feasibility for "late-stage modification" make this protocol very promising. Mechanistic studies including DFT calculation demonstrate a novel 1,2-hydride shift process for this novel nitrogenation reaction.

SUBMITTER: Huang X

PROVIDER: S-EPMC6054104 | biostudies-literature | 2015 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper-catalyzed direct transformation of simple alkynes to alkenyl nitriles via aerobic oxidative N-incorporation.

Huang Xiaoqiang X Li Xinyao X Jiao Ning N

Chemical science 20150720 11

A novel direct transformation of aliphatic terminal alkynes to alkenyl nitriles through the incorporation of a nitrogen atom into the simple hydrocarbons has been reported. The usage of inexpensive copper catalyst, O2 as the sole oxidant, broad substrate scope as well as feasibility for "late-stage modification" make this protocol very promising. Mechanistic studies including DFT calculation demonstrate a novel 1,2-hydride shift process for this novel nitrogenation reaction. ...[more]

PMID: 30090253

Similar Datasets

Direct Metal-Free Transformation of Alkynes to Nitriles: Computational Evidence for the Precise Reaction Mechanism.

Project description:Density functional theory calculations elucidated the precise reaction mechanism for the conversion of diphenylacetylenes into benzonitriles involving the cleavage of the triple C≡C bond, with N-iodosuccinimide (NIS) as an oxidant and trimethylsilyl azide (TMSN3) as a nitrogen donor. The reaction requires six steps with the activation barrier ΔG‡ = 33.5 kcal mol-1 and a highly exergonic reaction free-energy ΔGR = -191.9 kcal mol-1 in MeCN. Reaction profiles agree with several experimental observations, offering evidence for the formation of molecular I2, interpreting the necessity to increase the temperature to finalize the reaction, and revealing thermodynamic aspects allowing higher yields for alkynes with para-electron-donating groups. In addition, the proposed mechanism indicates usefulness of this concept for both internal and terminal alkynes, eliminates the option to replace NIS by its Cl- or Br-analogues, and strongly promotes NaN3 as an alternative to TMSN3. Lastly, our results advise increasing the solvent polarity as another route to advance this metal-free strategy towards more efficient processes.

| S-EPMC8004279 | biostudies-literature

Copper-catalyzed transformation of alkyl nitriles to N-arylacetamide using diaryliodonium salts.

Project description:This work reports a simple and efficient method for the copper-catalyzed redox-neutral transformation of alkyl nitriles using eco-friendly diaryliodonium salts and leading to N-arylacetamides. The method features high efficiency, broad substrate scope and good functional group tolerance.

| S-EPMC9036411 | biostudies-literature

Rh-catalyzed transannulation of pyridotriazoles with alkynes and nitriles.

Project description: Not available

| S-EPMC3684435 | biostudies-literature

Cobalt-catalyzed hydrothiolation of alkynes for the diverse synthesis of branched alkenyl sulfides.

Project description:Alkenyl sulfides have gained increasing prominence in medicinal chemistry and materials. Hydrothiolation of alkynes for the diverse synthesis of alkenyl sulfides is an appealing method. Herein, we report a cobalt-catalyzed Markovnikov hydromethylthiolation of alkynes to afford branched alkenyl methylsulfanes with good yields and high regioselectivity. This method also enables the diverse synthesis of branched alkenyl sulfides. The reaction shows good functional group tolerance and could be scaled up. The mechanistic studies including control experiments, deuterium-labeling experiments, and Hammett plot indicated alkynes insertion followed by electrophilic thiolation pathway.

| S-EPMC11401953 | biostudies-literature

Iron(II) Phthalocyanine-Catalyzed Olefination of Aldehydes with Diazoacetonitrile: A Novel Approach to Construct Alkenyl Nitriles.

Project description:A novel synthetic approach to preparing alkenyl nitriles via the olefination of aldehydes with diazoacetonitrile catalyzed by iron(II) phthalocyanine in the presence of PPh3 has been developed. A broad variety of aldehydes are efficiently transformed into the corresponding products with the high yields of 75%-97%. And it is also suitable for its gram-scale preparation. The suggested mechanism involves the transformation of the phosphazine to ylide by iron(II) phthalocyanine.

| S-EPMC10809703 | biostudies-literature

Hydroalkylation of Alkynes: Functionalization of the Alkenyl Copper Intermediate through Single Electron Transfer Chemistry.

Project description:We have developed a method for the stereoselective coupling of terminal alkynes and α-bromo carbonyls to generate functionalized E-alkenes. The coupling is accomplished by merging the closed-shell hydrocupration of alkynes with the open-shell single electron transfer (SET) chemistry of the resulting alkenyl copper intermediate. We demonstrate that the reaction is compatible with various functional groups and can be performed in the presence of aryl bromides, alkyl chlorides, alkyl bromides, esters, nitriles, amides, and a wide range of nitrogen-containing heterocyclic compounds. Mechanistic studies provide evidence for SET oxidation of the alkenyl copper intermediate by an α-bromo ester as the key step that enables the cross coupling.

| S-EPMC8751476 | biostudies-literature

Rh-catalyzed aerobic oxidative cyclization of anilines, alkynes, and CO.

Project description:Transition-metal-catalyzed oxidative C-H cyclization of anilines has been an attractive and powerful strategy for the efficient construction of N-heterocycles. However, primary and tertiary anilines are rarely employed in this strategy due to the relative instability with strong oxidants or the presence of three C-N bonds. We describe here a novel Rh-catalyzed C-H cyclization of a wide range of anilines with alkynes and CO, using an aerobic oxidative protocol. Particularly, the simple primary anilines and readily prepared tertiary anilines could be easily converted to quinolin-2(1H)-ones, which are high value-added, biologically significant N-heterocycles, via C-N bond cleavage.

| S-EPMC5628386 | biostudies-literature

Copper-catalyzed dehydrogenative borylation of terminal alkynes with pinacolborane.

Project description:LCuOTf complexes [L = cyclic (alkyl)(amino)carbenes (CAACs) or N-heterocyclic carbenes (NHCs)] selectively promote the dehydrogenative borylation of C(sp)-H bonds at room temperature. It is shown that σ,π-bis(copper) acetylide and copper hydride complexes are the key catalytic species.

| S-EPMC5308285 | biostudies-literature

Highly Chemoselective Hydroboration of Alkynes and Nitriles Catalyzed by Group 4 Metal Amidophosphine-Borane Complexes.

Project description:We report a series of titanium and zirconium complexes supported by dianionic amidophosphine-borane ligands, synthesized by amine elimination and salt metathesis reactions. The TiIV complex [{Ph2P(BH3)N}2C6H4Ti(NMe2)2] (1) was obtained by the reaction between tetrakis-(dimethylamido)titanium(IV) and the protic aminophosphine-borane ligand [{Ph2P(BH3)NH}2C6H4] (LH2) at ambient temperature. Both the heteroleptic zirconium complexes-[η5-(C5H5)2Zr{Ph2P(BH3)N}2C6H4] (2) and [[{Ph2P(BH3)N}2C6H4]ZrCl2] (3)-and the homoleptic zirconium complex [[{Ph2P(BH3)N}2C6H4]2Zr] (4) were obtained in good yield by the salt metathesis reaction of either zirconocene dichloride [η5-(C5H5)2ZrCl2] or zirconium tetrachloride with the dilithium salt of the ligand [{Ph2P(BH3)NLi}2C6H4] (LLi2), which was prepared in situ. The molecular structures of the complexes 1, 2, and 4 in their solid states were confirmed by single-crystal X-ray diffraction analysis. Of these complexes, only titanium complex 1 acts as an effective catalyst for the facile hydroboration of terminal alkynes, yielding exclusive E-isomers. The hydroboration of organic nitriles yielded diborylamines with a broad substrate scope, including broad functional group compatibility. The mechanism of hydroboration occurs through the formation of titanium hydride as an active species.

| S-EPMC6990649 | biostudies-literature

Predictable and regioselective insertion of internal unsymmetrical alkynes in rhodium-catalyzed cycloadditions with alkenyl isocyanates.

Project description:A regioselective, rhodium-catalyzed cycloaddition between a variety of internal, unsymmetrical alkynes is described. We document the impact of both steric and electronic properties of the alkyne on reaction course, efficiency, and enantioselectivity. The substituent that better stabilizes a positive charge or the larger group, all else being equal, inserts distal to the carbonyl moiety in a predictable and controllable fashion. The reaction scope is broad and the enantioselectivities are high, providing an "instruction manual" for substrate choice when utilizing this reaction as a synthetic tool.

| S-EPMC2737069 | biostudies-literature