Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of Functionalized Isoquinolone Derivatives via Rh(III)-Catalyzed [4+2]-Annulation of Benzamides with Internal Acetylene-Containing α-CF3-α-Amino Carboxylates.

ABSTRACT: A convenient pathway to a new series of α-CF3-substituted α-amino acid derivatives bearing pharmacophore isoquinolone core in their backbone has been developed. The method is based on [4+2]-annulation of N-(pivaloyloxy) aryl amides with orthogonally protected internal acetylene-containing α-amino carboxylates under Rh(III)-catalysis. The target annulation products can be easily transformed into valuable isoquinoline derivatives via a successive aromatization/cross-coupling operation.

SUBMITTER: Vorobyeva DV

PROVIDER: S-EPMC9736582 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of Functionalized Isoquinolone Derivatives via Rh(III)-Catalyzed [4+2]-Annulation of Benzamides with Internal Acetylene-Containing α-CF3-α-Amino Carboxylates.

Vorobyeva Daria V DV Petropavlovskikh Dmitry A DA Godovikov Ivan A IA Dolgushin Fedor M FM Osipov Sergey N SN

Molecules (Basel, Switzerland) 20221202 23

A convenient pathway to a new series of α-CF3-substituted α-amino acid derivatives bearing pharmacophore isoquinolone core in their backbone has been developed. The method is based on [4+2]-annulation of N-(pivaloyloxy) aryl amides with orthogonally protected internal acetylene-containing α-amino carboxylates under Rh(III)-catalysis. The target annulation products can be easily transformed into valuable isoquinoline derivatives via a successive aromatization/cross-coupling oper ...[more]

PMID: 36500580

Similar Datasets

Rh(III)-Catalyzed Annulation of Boc-Protected Benzamides with Diazo Compounds: Approach to Isocoumarins.

Project description:A mild rhodium-catalyzed annulation of Boc-protected benzamides with diazo compounds via C-C/C-O bond formation has been explored. In the presence of [Cp*RhCl₂]₂, AgSbF₆ and Cs₂CO₃, Boc-protected benzamides can be effectively annulated to yield isocoumarins in 0.5⁻2 h.

| S-EPMC6429621 | 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

Convenient Synthesis of Functionalized Cyclopropa[c]coumarin-1a-carboxylates.

Project description:A simple method has been developed for the synthesis of cyclopropa[c]coumarins, which belong to the donor-acceptor cyclopropane family and, therefore, are promising substrates for the preparation of chromene-based fine chemicals. The method, based on the acetic acid-induced intramolecular transesterification of 2-arylcyclopropane-1,1-dicarboxylates, was found to be efficient for substrates containing hydroxy group directly attached to the aromatic ring.

| S-EPMC6337311 | biostudies-literature

Combining the Ugi-azide multicomponent reaction and rhodium(III)-catalyzed annulation for the synthesis of tetrazole-isoquinolone/pyridone hybrids.

Project description:An efficient sequence based on the Ugi-azide reaction and rhodium(III)-catalyzed intermolecular annulation has been established for the preparation of tetrazole-isoquinolone/pyridone hybrids. Several N-acylaminomethyltetrazoles were reacted with arylacetylenes to form the hybrid products in moderate to very good yields. The method relies on the capacity of the rhodium catalyst to promote C(sp2)-H activation in the presence of a suitable directing group. The Ugi-azide reaction provides broad molecular diversity and enables the introduction of the tetrazole moiety, which may further assist the catalytic reaction by coordinating the metal center. The scope of the isoquinolones is very wide and may be extended to the preparation of complex compounds having heterocyclic moieties such as pyridone, furan, thiophene and pyrrole, as well as the corresponding benzo-fused derivatives. The developed procedure is simple, reproducible and does not require inert conditions.

| S-EPMC6808192 | biostudies-literature

Regio- and Stereoselective Synthesis of the Core Structure of Hexahydrobenzo[c]phenanthridine Alkaloids via Redox-Neutral Cp*Rh(III)-Catalyzed C-H/N-H Annulation of Cyclic Alkenes with Benzamides.

Project description:A highly stereo- and regioselective synthesis of the core skeleton of hexahydrobenzo[c]phenanthridine-type alkaloids is reported herein for the first time. A wide range of substrate scope, excellent functional group tolerance, and good to excellent yields were observed. This protocol gives very concise and efficient access to the core skeleton of chelidonine alkaloids as compared to the earlier approaches.

| S-EPMC7513371 | biostudies-literature

Rh(II)-mediated domino [4 + 1]-annulation of α-cyanothioacetamides using diazoesters: A new entry for the synthesis of multisubstituted thiophenes.

Project description:A new approach towards the synthesis of multisubstituted thiophenes is elaborated based on Rh(II)-catalyzed domino reactions of acyclic diazoesters with α-cyanothioacetamides. It provides a way for the preparation of 5-amino-3-(alkoxycarbonylamino)thiophene-2-carboxylates, 2-(5-amino-2-methoxycarbonylthiophene-3-yl)aminomalonates and (2-cyano-5-aminothiophene-3-yl)carbamates with the preparative yields of up to 67%. It was also shown that α-cyanothioacetamides easily interact with dirhodium carboxylates to give rather stable 2:1 complexes, resulting in an evident decrease in the efficiency of the catalytic process at moderate temperatures (20-30 °C).

| S-EPMC5727864 | biostudies-literature

Direct access to multi-functionalized benzenes via [4 + 2] annulation of α-cyano-β-methylenones and α,β-unsaturated aldehydes.

Project description:An efficient [4 + 2] benzannulation of α-cyano-β-methylenones and α,β-unsaturated aldehydes was achieved under metal-free reaction conditions selectively delivering a wide range of polyfunctional benzenes in high yields respectively (up to 94% yield).

| S-EPMC9055964 | biostudies-literature

One-pot construction of diverse and functionalized isochromenoquinolinediones by Rh(iii)-catalyzed annulation of unprotected arylamides with 3-diazoquinolinediones and their application for fluorescence sensor.

Project description:A facile and efficient Rh(iii)-catalyzed annulation of arylamides with 3-diazoquinolinediones for the construction of diverse and highly functionalized isochromenoquinolinediones is described. Furthermore, the methodology is applicable for delivering various relevant molecules such as pyridopyranoquinolindiones, thienopyranoquinolinones, and indolopyranoquinolinone. The reaction proceeds via cascade C-H activation, carbene insertion, and intramolecular lactonization. The reaction exhibits high atom economy, good functional group tolerance, and high regioselectivity. The synthesized compound can also behave as a potent fluorescence sensor for Fe3+ ion.

| S-EPMC9064558 | biostudies-literature

An unusual endo-selective C-H hydroarylationof norbornene by the Rh(I)-catalyzed reactionof benzamides.

Project description:Hydroarylation is an environmentally attractive strategy which incorporates all of the atoms contained in the substrates into the desired products. Almost all the hydroarylations of norbornene reported to date involve an exo-selective reaction. Here we show the endo-selective hydroarylation of norbornene in the Rh(I)-catalyzed reaction of aromatic amides. The addition of sterically bulky carboxylic acids enhances the endo-selectivity of the reaction. The results of deuterium-labeling experiments show that both the ortho-carbon and the ortho-hydrogen atoms of aromatic amides were attached to the same carbon atom of the norbornane skeleton in the hydroarylation product. These results clearly suggest that hydrometalation or carbometalation, which are commonly accepted mechanisms for the catalytic hydroarylation of C-H bonds, are not involved as the key step in the present reaction, and suggest that the reaction involves a rhodium carbene complex generated from norbornene as the key intermediate.

| S-EPMC5682280 | biostudies-literature

Co-catalyzed ortho-C-H functionalization/annulation of arenes and alkenes with alkynylsilanes: access to isoquinolone and pyridone motifs.

Project description:A method for cobalt-catalyzed ortho-C-H functionalization annulation of arenes and alkenes with alkynylsilanes assisted by 8-aminoquinolyl auxiliary has been described. Alkynylsilanes were employed as the coupling partners to react with a broad range of benzamides and acrylamides, affording the corresponding isoquinolone and pyridone derivatives in moderate to high yields. It is worth noting that the silyl group in the final products can be retained or removed by switching the reaction conditions.

| S-EPMC9072155 | biostudies-literature