Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Aerobic Metal-Free Dioxygenation of Alkenes with tert-Butyl Nitrite and N-Hydroxylamines.

ABSTRACT: Metal-free dioxygenation of alkenes with tert-butyl nitrite and N-hydroxylamines (N-hydroxyphthalimide, N-hydroxybenzotriazole, and N-hydroxysuccinimide) is described to produce ?-aminoxy nitrate esters using air as the oxidant. These organic nitrates can be readily converted into 1,2-diols and 1,2-diketone with broad substrate scope and functional group diversity.

SUBMITTER: Bag R

PROVIDER: S-EPMC6644589 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Aerobic Metal-Free Dioxygenation of Alkenes with tert-Butyl Nitrite and N-Hydroxylamines.

Bag Raghunath R Sar Dinabandhu D Punniyamurthy Tharmalingam T

ACS omega 20170929 9

Metal-free dioxygenation of alkenes with tert-butyl nitrite and N-hydroxylamines (N-hydroxyphthalimide, N-hydroxybenzotriazole, and N-hydroxysuccinimide) is described to produce β-aminoxy nitrate esters using air as the oxidant. These organic nitrates can be readily converted into 1,2-diols and 1,2-diketone with broad substrate scope and functional group diversity. ...[more]

PMID: 31457873

Similar Datasets

Aerobic radical multifunctionalization of alkenes using tert-butyl nitrite and water.

Project description:Water induces a change in the product of radical multifunctionalization reactions of aliphatic alkenes involving an sp(3) C-H functionalization by an 1,5-hydrogen shift using tert-butyl nitrite and molecular oxygen. The reaction without water, reported previously, gives nitrated ?-lactols, whereas the reaction in the presence of water produces 4-hydroxy-5-nitropentyl nitrate or 4-hydroxy-3-nitropentyl nitrate derivatives.

| S-EPMC3778400 | biostudies-literature

Aerobic palladium-catalyzed dioxygenation of alkenes enabled by catalytic nitrite.

Project description:Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups were tolerated, and high yields (up to 94 %) were observed with many substrates, also for a multigram-scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was demonstrated to be a potential intermediate in the catalytic cycle. Furthermore, the reductive elimination event was probed with (18) O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.

| S-EPMC4285779 | biostudies-literature

Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes.

Project description:Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

| S-EPMC5056438 | biostudies-literature

[2 + 2 + 1] Cycloaddition of N-tosylhydrazones, tert-butyl nitrite and alkenes: a general and practical access to isoxazolines.

Project description:N-Tosylhydrazones have proven to be versatile synthons over the past several decades. However, to our knowledge, the construction of isoxazolines based on N-tosylhydrazones has not been examined. Herein, we report the first demonstrations of [2 + 2 + 1] cycloaddition reactions that allow the facile synthesis of isoxazolines, employing N-tosylhydrazones, tert-butyl nitrite (TBN) and alkenes as reactants. This process represents a new type of cycloaddition reaction with a distinct mechanism that does not involve the participation of nitrile oxides. This approach is both general and practical and exhibits a wide substrate scope, nearly universal functional group compatibility, tolerance of moisture and air, the potential for functionalization of complex bioactive molecules and is readily scaled up. Both control experiments and theoretical calculations indicate that this transformation proceeds via the in situ generation of a nitronate from the coupling of N-tosylhydrazone and TBN, followed by cycloaddition with an alkene and subsequent elimination of a tert-butyloxy group to give the desired isoxazoline.

| S-EPMC8293996 | biostudies-literature

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines.

Project description:A copper-catalyzed regio- and stereoselective diamination of unactivated alkenes has been developed with O-acylhydroxylamines as electrophilic nitrogen sources and oxidants. This method provides the first example of metal-catalyzed alkene diamination for directly installing an electron-rich amino group and extends the diamination scope for the synthesis of diverse 1,2-diamines. It offers a rapid and efficient approach to construct a wide range of 1,2-diamines that are an important structural motif in organic synthesis, medicines, catalysts and ligands.

| S-EPMC5707484 | biostudies-literature

Chemoselective nitration of phenols with tert-butyl nitrite in solution and on solid support.

Project description:tert-Butyl nitrite was identified as a safe and chemoselective nitrating agent that provides preferentially mononitro derivatives of phenolic substrates in the presence of potentially competitive functional groups. On the basis of our control experiments, we propose that the reaction proceeds through the formation of O-nitrosyl intermediates prior to C-nitration via homolysis and oxidation. The reported nitration method is compatible with tyrosine-containing peptides on solid support in the synthesis of fluorogenic substrates for characterization of proteases.

| S-EPMC2758266 | biostudies-literature

Oxidative Dehydrogenation of Hydrazobenzenes toward Azo Compounds Catalyzed by tert-Butyl Nitrite in EtOH.

Project description:We describe a tert-butyl nitrite-catalyzed oxidative dehydrogenation of hydrazobenzenes for producing azobenzenes. This method proceeds at ambient temperature and under an atmospheric environment by employing eco-friendly EtOH as the medium, representing a mild, general route to the synthesis of various symmetrical and nonsymmetrical azobenzenes in excellent yields with broad functional group tolerance.

| S-EPMC7659151 | biostudies-literature

Transition Metal-Free 1,2-Carboboration of Unactivated Alkenes.

Project description:A method for transition metal-free 1,2-carboboration of unactivated alkenes with bis(catecholato)diboron as the boron source in combination with alkyl halides as the alkyl component is introduced. The three-component reaction proceeds via a radical pathway on a broad range of unactivated alkenes, and the 1,2-carboboration products serve as valuable synthetic building blocks. Density functional theory calculations provide insights into the mechanism.

| S-EPMC6014685 | biostudies-literature

Metal-Free Direct C-H Cyanation of Alkenes.

Project description:A metal-free and direct alkene C-H cyanation is described. Directing groups are not required and the mechanism involves electrophilic activation of the alkene by a cyano iodine(III) species generated in situ from a [bis(trifluoroacetoxy)iodo]arene and trimethylsilyl cyanide as the cyanide source. This C-H functionalization can be conducted on gram scale, and for noncyclic 1,1- and 1,2-disubstuted alkenes high stereoselectivity is achieved, thus rendering the method highly valuable.

| S-EPMC6175092 | biostudies-literature

(R)-N-{2-tert-Butyl-2-[(R)-tert-butyl-sulfonamido]ethylidene}-tert-butane-sulfonamide.

Project description:The title compound, C(14)H(30)N(2)O(2)S(2), is the product of the monoaddition reaction of tert-butyl magnesium chloride with bis-[(R)-N-tert-butanesulfinyl]ethanediimine. There are two almost identical mol-ecules in the asymmetric unit, the mol-ecular conformation of which is stabilized by an intra-molecular N-H?N hydrogen bond.

| S-EPMC2959383 | biostudies-literature