Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Directed Palladium-Catalyzed Acetoxylation of Indolines. Total Synthesis of N-Benzoylcylindrocarine.

ABSTRACT: We describe a palladium-catalyzed C7-acetoxylation of indolines with a range of amide directing groups. While a variety of substituents are tolerated on the indoline-core and the N1-acyl group, the acetoxylation is most sensitive to the C2- and C6-indoline substituents. The practicality of this indoline C7-acetoxylation is demonstrated using a cinnamamide substrate on a mmol scale. Several N1-acyl groups, including those present in natural alkaloids, guide C7-acetoxylation of indoline substrates over a competitive C5-oxidation. The application of this chemistry allowed for the first synthesis of N-benzoylcylindrocarine by late-stage C17-acetoxylation of N-benzoylfendleridine.

SUBMITTER: Flynn KM

PROVIDER: S-EPMC9020104 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Directed Palladium-Catalyzed Acetoxylation of Indolines. Total Synthesis of <i>N</i>-Benzoylcylindrocarine.

Flynn Kristen M KM White Kolby L KL Movassaghi Mohammad M

The Journal of organic chemistry 20220125 5

We describe a palladium-catalyzed C7-acetoxylation of indolines with a range of amide directing groups. While a variety of substituents are tolerated on the indoline-core and the N1-acyl group, the acetoxylation is most sensitive to the C2- and C6-indoline substituents. The practicality of this indoline C7-acetoxylation is demonstrated using a cinnamamide substrate on a mmol scale. Several N1-acyl groups, including those present in natural alkaloids, guide C7-acetoxylation of indoline substrates ...[more]

PMID: 35076246

Similar Datasets

Palladium-Catalyzed C-H Bond Acetoxylation via Electrochemical Oxidation.

Project description:Here we describe the development of a method for the Pd-catalyzed electrochemical acetoxylation of C-H bonds. The oxidation step of the catalytic cycle is probed through cyclic voltammetry and bulk electrolysis studies of a preformed palladacycle of 8-methylquinoline. A catalytic system for C-H acetoxylation is then developed and optimized with respect to the cell configuration, rate of oxidation, and chemistry at the counter electrode. This transformation is then applied to substrates containing various directing groups and to the acetoxylation of both C(sp2)-H and C(sp3)-H bonds.

| S-EPMC5772685 | biostudies-literature

Palladium-Catalyzed Acetoxylation of γ-Dehydro-aryl-himachalene: The Synthesis of a Novel Allylic Acetoxylated Sesquiterpene and a π-Allyl Palladium(II) Complex.

Project description:Allylic oxygenated derivatives of himachalenes are highly valued molecules due to their potential applications in perfumery, cosmetics, and pharmaceuticals. Previous attempts at catalyzed allylic oxidation of himachalenes led to the formation of a very stable η3-allyl palladium complex, preventing any further reaction development. Herein, we present the first successful palladium-catalyzed synthesis of a novel allylic acetoxylated derivative of himachalenes. This reaction was achieved by incorporating an aromatic ring into the substrate structure. The resulting intermediate complex was isolated and characterized using nuclear magnetic resonance spectroscopy and X-ray crystallography. Density functional theory (DFT) calculations were performed to compare the reactivity of the newly synthesized complex with previously reported ones. The theoretical results confirm that the introduction of an aromatic ring enhances the reactivity of the η³-allyl palladium complex, thereby facilitating the desired transformation.

| S-EPMC11547928 | biostudies-literature

Total Synthesis of Cyclopiamide A Using Palladium-Catalyzed Domino Cyclization.

Project description:Total synthesis of cyclopiamide A was accomplished using a palladium-catalyzed domino cyclization. Three rings in the tetracyclic skeleton of cyclopiamide A were constructed in a one-step domino reaction incorporating double carbopalladation and C-H activation.

| S-EPMC7660198 | biostudies-literature

Palladium(II)-Catalyzed Tandem Oxidative Acetoxylation/ortho C-H Activation/Carbocyclization of Arylallenes.

Project description:Herein we report an example of tandem oxidative acetoxylation/carbocyclization of arylallenes 1 using Pd(OAc)2. The catalytic protocol is highly selective and provides access to new C-C and C-O bonds leading to a carbocyclization. The reaction proceeds via C-H activation by Pd. Mechanistic investigations show that the C-H activation is not the rate-limiting step and indicate that the reaction proceeds via acetoxylation of the allene.

| S-EPMC4557776 | biostudies-literature

Formal aromaticity transfer for palladium-catalyzed coupling between phenols and pyrrolidines/indolines.

Project description:We herein describe a palladium-catalyzed formal aromaticity transfer coupling reaction between phenols and pyrrolidines or indolines to generate the corresponding N-cyclohexyl pyrroles or indoles. In this transformation, the aromaticity of phenols is formally passed on to the pyrrolidine or indoline units. Substituted phenols thus can serve as latent cyclohexyl equivalents for the fast construction of various N-cyclohexyl pyrroles and indoles.

| S-EPMC5642148 | biostudies-literature

Total Synthesis of (-)-Aspidospermidine via an Enantioselective Palladium-Catalyzed Allylic Substitution Strategy.

Project description:A total synthesis of (-)-aspidospermidine via an enantioselective Pd-catalyzed allylic substitution strategy is reported. This represents the first application of a Pd-catalyzed allylic substitution with a 3-substituted indole derivative in the synthesis of Aspidosperma alkaloids. In our synthetic route, the allylic substitution reaction was the stereo defining step. The pentacyclic framework was then constructed in a fully diastereoselective sequence. This culminated in the shortest enantioselective synthesis of aspidospermidine reported to date, in seven linear steps.

| S-EPMC11574843 | biostudies-literature

Mechanistic comparison between Pd-catalyzed ligand-directed C-H chlorination and C-H acetoxylation.

Project description:This communication describes detailed investigations of the mechanism of the Pd-catalyzed C-H chlorination and acetoxylation of 2-o-tolylpyridine. Under the conditions examined, both reactions proceed via rate-limiting cyclopalladation. However, substrate and catalyst order as well as Hammett data indicate that the intimate mechanism of cyclopalladation differs significantly between PdCl2-catalyzed chlorination and Pd(OAc)2-catalyzed acetoxylation.

| S-EPMC2778044 | biostudies-literature

Total Synthesis of (-)-Xylogranatopyridine B via a Palladium-Catalyzed Oxidative Stannylation of Enones.

Project description:We report a total synthesis of the pyridine-containing limonoid alkaloid (-)-xylogranatopyridine B in 11 steps from commercially available dihydrocarvone. The central pyridine ring was assembled by a late-stage fragment coupling approach employing a modified Liebeskind pyridine synthesis. One fragment was prepared by an allyl-palladium catalyzed oxidative enone β-stannylation, in which the key bimetallic β-stannyl palladium enolate intermediate undergoes a β-hydride elimination. This methodology also allowed introduction of alkyl and silyl groups to the β-position of enones.

| S-EPMC6499388 | biostudies-literature

Enantioselective synthesis of α-quaternary Mannich adducts by palladium-catalyzed allylic alkylation: total synthesis of (+)-sibirinine.

Project description:A catalytic enantioselective method for the synthesis of α-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of "thermodynamic" enolates of substrates possessing additional enolizable positions and acidic protons. Palladium-catalyzed decarboxylative allylic alkylation enables the enantioselective synthesis of five-, six-, and seven-membered ketone, lactam, and other heterocyclic systems. The mild reaction conditions are notable given the acidic free N-H groups and high functional group tolerance in each of the substrates. The utility of this method is highlighted in the first total synthesis of (+)-sibirinine.

| S-EPMC4311947 | biostudies-literature

Selective Iron Catalyzed Synthesis of N-Alkylated Indolines and Indoles.

Project description:Whereas iron catalysts usually promote catalyzed C3-alkylation of indole derivatives via a borrowing-hydrogen methodology using alcohols as the electrophilic partners, this contribution shows how to switch the selectivity towards N-alkylation. Thus, starting from indoline derivatives, N-alkylation was efficiently performed using a tricarbonyl(cyclopentadienone) iron complex as the catalyst in trifluoroethanol in the presence of alcohols leading to the corresponding N-alkylated indoline derivatives in 31-99 % yields (28 examples). The one-pot, two-step strategy for the selective N-alkylation of indolines is completed by an oxidation to give the corresponding N-alkylated indoles in 31-90 % yields (15 examples). This unprecedented oxidation methodology involves an iron salt catalyst associated with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and a stoichiometric amount of t-BuOOH at room temperature.

| S-EPMC9796591 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data