Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rh-Catalyzed Cascade C-H Activation/Annulation of N-Hydroxybenzamides and Propargylic Acetates for Modular Access to Isoquinolones.

ABSTRACT: A sequential Rh(III)-catalyzed C-H activation/annulation of N-hydroxybenzamides with propargylic acetates leading to the formation of NH-free isoquinolones is described. This reaction proceeds through a sequential C-H activation/alkyne insertion/intramolecular annulation/N-O bond cleavage procedure, affording a broad spectrum of products with diverse substituents in moderate-to-excellent yields. Notably, this protocol features the simultaneous formation of two new C-C/C-N bonds and one heterocycle in one pot with the release of water as the sole byproduct.

SUBMITTER: Fang T

PROVIDER: S-EPMC9740102 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Rh-Catalyzed Cascade C-H Activation/Annulation of N-Hydroxybenzamides and Propargylic Acetates for Modular Access to Isoquinolones.

Fang Taibei T Zhang Shiwen S Ye Qingqing Q Kong Shuwen S Yang Tingting T Tang Kaijie K He Xinwei X Shang Yongjia Y

Molecules (Basel, Switzerland) 20221205 23

A sequential Rh(III)-catalyzed C-H activation/annulation of N-hydroxybenzamides with propargylic acetates leading to the formation of NH-free isoquinolones is described. This reaction proceeds through a sequential C-H activation/alkyne insertion/intramolecular annulation/N-O bond cleavage procedure, affording a broad spectrum of products with diverse substituents in moderate-to-excellent yields. Notably, this protocol features the simultaneous formation of two new C-C/C-N bonds and one he ...[more]

PMID: 36500644

Similar Datasets

Practical synthesis of isocoumarins via Rh(III)-catalyzed C-H activation/annulation cascade.

Project description:Herein, we report an unprecedented Rh(III)-catalyzed C-H activation/annulation cascade of readily available enaminones with iodonium ylides towards the convenient synthesis of isocoumarins. This coupling system proceeds in useful chemical yields (up to 93%) via a cascade C-H activation, Rh-carbenoid migratory insertion and acid-promoted intramolecular annulation. The success of gram-scale reaction and diverse functionalization of isocoumarins demonstrated the synthetic utility of this protocol.

| S-EPMC9907013 | biostudies-literature

Rh(iii)-Catalyzed [5 + 1] annulation of 2-alkenylanilides and 2-alkenylphenols with allenyl acetates.

Project description:Herein, we report a mild and highly regioselective Rh(iii)-catalyzed non-oxidative [5 + 1] vinylic C-H annulation of 2-alkenylanilides with allenyl acetates, which has been elusive so far. The reaction proceeds via vinylic C-H activation, regioselective 2,3-migratory insertion, β-oxy elimination followed by nucleophilic cyclization to get direct access to 1,2-dihydroquinoline derivatives. The strategy was also successfully extended to C-H activation of 2-alkenylphenols for constructing chromene derivatives. In the overall [5 + 1] annulation, the allene serves as a one carbon unit. The acetate group on the allene is found to be crucial both for controlling the regio- and chemoselectivity of the reaction and also for facilitating β-oxy elimination. The methodology was scalable and also further extended towards late stage functionalization of various natural products.

| S-EPMC8848808 | biostudies-literature

Dual C-H activation: Rh(iii)-catalyzed cascade π-extended annulation of 2-arylindole with benzoquinone.

Project description:A rhodium-catalyzed, N-H free indole directed cyclization reaction of benzoquinone via a dual C-H activation strategy is disclosed. This protocol has a good functional group tolerance and affords useful indole-fused heterocylces. Besides, it is insensitive to moisture, commercially available solvent can be directly used and work quite well for this transformation.

| S-EPMC8697334 | biostudies-literature

Rh(iii)-catalyzed regioselective C-H activation dialkenylation/annulation cascade for rapid access to 6H-isoindolo[2,1-a]indole.

Project description:6H-isoindolo[2,1-a]indoles were accessed via a Rh(iii)-catalyzed N-H free indole directed C-H activation dialkenylation/annulation cascade in moderate to excellent yields. This protocol also features: reaction procedures that are insensitive to air and moisture, excellent regioselectivity and good functional group tolerance.

| S-EPMC9037025 | biostudies-literature

Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates.

Project description:A novel iron-catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di-, tri- and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-SN 2' displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was further substantiated by transformations of the obtained allenylboronates including oxidation and propargylation.

| S-EPMC10099795 | biostudies-literature

Lewis-Acid-Catalyzed (3+2) Annulation of 2-Indolylmethanols with Propargylic Alcohols to Access Cyclopenta[b]indoles.

Project description:Herein, a Sc(OTf)3-catalyzed (3+2) annulation of 2-indolylmethanols with propargylic alcohols is reported. The reaction proceeds via a Friedel-Crafts-type allenylation/5-exo-annulation cascade. In the reaction, 2-indolylmethanol is used as a three-carbon synthon, and propargyl alcohol is used as a two-carbon synthon. This method provides a direct and high-yield pathway for synthetically useful cyclopenta[b]indoles. In general, the method features easily accessible substrates with broad scope and generality, the formation of multiple bonds with high efficiency, and easy scale-up.

| S-EPMC10974089 | biostudies-literature

An expeditious FeCl3-catalyzed cascade 1,4-conjugate addition/annulation/1,5-H shift sequence for modular access of all-pyrano-moiety-substituted chromenes.

Project description:ortho-Alkynyl quinone methides are well-known four-atom synthons for direct [4 + n] cycloaddition in constructing useful oxa-heterocyclic compounds owing to their high reactivity as well as the thermodynamically favored aromatization nature of this process. Herein we report an operationally simple and eco-friendly protocol for the modular and regioselective access of (E)-4-(vinyl or aryl or alkynyl)iminochromenes from propargylamines and S-methylated β-ketothioamides in the presence of FeCl3, and particularly under undried acetonitrile and air atmosphere conditions. This method exhibits a broad substrate scope and displays nice functional group compatibility, thus providing an efficient access of 3,4-disubstituted iminochromenes.

| S-EPMC9682991 | biostudies-literature

Synthesis of CF3-Containing Spiro-[Indene-Proline] Derivatives via Rh(III)-Catalyzed C-H Activation/Annulation.

Project description:An efficient method of accessing new CF3-containing spiro-[indene-proline] derivatives has been developed based on a Cp*Rh(III)-catalyzed tandem C-H activation/[3+2]-annulation reaction of 5-aryl-2-(trifluoromethyl)-3,4-dihydro-2H-pyrrole-2-carboxylates with alkynes. An important feature of this spiro annulation process is the feasibility of dehydroproline moiety to act as a directing group in the selective activation of the aromatic C-H bond.

| S-EPMC10708072 | biostudies-literature

N-Heterocyclic Carbene Catalyzed Enantioselective Annulation of Benzothiazolyl Ethyl Acetates with 2-Bromoenals.

Project description:An N-heterocyclic carbene catalyzed enantioselective [3+3] annulation of benzothiazolyl acetates with 2-bromoenals has been developed. The protocol provides a direct asymmetric synthesis of dihydro-1H-benzothiazolopyridinones in good to very good yields and medium ee values. In many cases, the virtually enantiopure heterocycles are available through a single recrystallization (99% ee).

| S-EPMC4702349 | biostudies-literature

Rh(II)/Pd(0) Dual-Catalyzed Regio-Divergent Three-Component Propargylic Substitution.

Project description:Regio-divergent propargylic substitution to generate functionally diverse products from identical starting materials remains a formidable challenge, probably due to the unpredictable regiochemical complexity. In practically, the synthesis of α-quaternary propargylic-substituted products is still much less developed, and preprepared nucleophiles are generally applied in this type of reaction with propargylic substrates, which limits the reaction efficiency and diversity of the obtained products. Herein, we disclose unprecedented three-component propargylic substitution of α-diazo esters with amines and propargylic carbonates under dirhodium/palladium dual catalysis. The key to the success of this multicomponent propargylic substitution is to avoid two-component side reactions through a tandem process of dirhodium(II)-catalyzed carbene insertion and palladium-catalyzed regiodivergent propargylic substitution. The judicious selection of a diphosphine (dppf) or monophosphine (tBuBrettphos) as the ligand is crucial for the reaction to generate different products in a switchable way, α-quaternary 1,3-dienyl or propargylated products, with high regio- and chemoselectivities.

| S-EPMC10598837 | biostudies-literature