Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Exploring Short and Efficient Synthetic Routes Using Titanocene(III)-Catalyzed Reactions: Total Synthesis of Natural Meroterpenes with Trisubstituted Unsaturations.

ABSTRACT: The stereo- and regioselective total syntheses of OMe derivatives of the scarce bioactive meroterpenoids makassaric acid (1) and fascioquinol B (2) have been accomplished. The synthetic sequences are based on the following three efficient and selective catalytic reactions: Cu-catalyzed addition of Grignard compounds to an epoxide; a regioselective Barbier-type reaction, catalyzed by Cp₂TiCl; and regio- and stereoselective bioinspired cyclization, also catalyzed by Cp₂TiCl. These three key processes allow us to obtain the main skeletons of 1 and 2 in a few steps. The valuable synthetic proposal shown in this work provides fast access to scarce, structurally complex meroterpenes with promising biological activities, which are a sustainable source for later studies and applications in medicine.

SUBMITTER: Rosales J

PROVIDER: S-EPMC9031794 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Exploring Short and Efficient Synthetic Routes Using Titanocene(III)-Catalyzed Reactions: Total Synthesis of Natural Meroterpenes with Trisubstituted Unsaturations.

Rosales Jennifer J Cabrera Gustavo G Justicia José J

Molecules (Basel, Switzerland) 20220408 8

The stereo- and regioselective total syntheses of OMe derivatives of the scarce bioactive meroterpenoids makassaric acid (1) and fascioquinol B (2) have been accomplished. The synthetic sequences are based on the following three efficient and selective catalytic reactions: Cu-catalyzed addition of Grignard compounds to an epoxide; a regioselective Barbier-type reaction, catalyzed by Cp2TiCl; and regio- and stereoselective bioinspired cyclization, also catalyzed by Cp<sub ...[more]

PMID: 35458598

Similar Datasets

Titanocene(III)-Catalyzed Precision Deuteration of Epoxides.

Project description:We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often excellent diastereoselectivity after desilylation. The key to the success of the reaction is a novel activation method of Cp2 TiCl2 and (tBuC5 H4 )2 TiCl2 with BnMgBr and PhSiD3 to provide [(RC5 H4 )2 Ti(III)D] without isotope scrambling. It was developed after discovering an off-cycle scrambling with the previously described method. Our precision deuteration can be applied to the synthesis of drug precursors and highlights the power of combining radical chemistry with organometallic catalysis.

| S-EPMC9305931 | biostudies-literature

Titanocene(III)-catalyzed formation of indolines and azaindolines.

Project description:Reductive cyclization of epoxides tethered to substituted anilines and aminopyridines in the presence of 3 mol % of titanocene dichloride and stoichiometric manganese metal promotes a radical annulation to form 3,3-disubstituted indolines and azaindolines.

| S-EPMC5467310 | biostudies-literature

Bi(III)-Catalyzed Enantioselective Allylation Reactions of Ketimines.

Project description:Chiral homoallylic amines not only are found in pharmaceutically relevant compounds but also serve as versatile building blocks for chemical synthesis. However, catalytic allylation of ketimines with allylboronates, an attractive approach to synthesize chiral homoallylic amine scaffolds remain scarce. Herein, we develop a highly enantioselective allylation of isatin-derived ketimines with boron allylation reagents catalyzed by a Bi(OAc)3-chiral phosphoric acid catalyst system. The reactions are remarkably efficient and mild, most of which were completed in less than an hour at room temperature with only 1/2 mol% (Bi(OAc)3/CPA) catalyst loading. A wide range of chiral 3-allyl 3-aminooxindoles were obtained in excellent yields and enantioselectivities. The synthetic utility was demonstrated by efficient formal synthesis of (+)-AG-041R and (-)-psychotriasine. Preliminary mechanism was studied by control experiments and theoretical calculations.

| S-EPMC6593186 | biostudies-literature

Gold-catalyzed tandem reactions of amide-aldehyde-alkyne coupling and cyclization-synthesis of 2,4,5-trisubstituted oxazoles.

Project description:We report the first cationic gold(i)-catalyzed one-pot reaction of amide, alkyne and aldehyde followed by cyclization, to successfully access highly substituted oxazoles derivatives in good yields. A single catalyst allows the occurring of this multi-step reaction atom- and step-economically, with water as the only theoretical side product.

| S-EPMC5950834 | biostudies-literature

Site-Selective Double and Tetracyclization Routes to Fused Polyheterocyclic Structures by Pd-Catalyzed Carbonylation Reactions.

Project description:In this contribution, we report novel palladium-catalyzed carbonylative cascade approaches to highly functionalized polyheterocyclic structures. The Pd-catalyzed carbonylative process involves the regioselective insertion of one to three CO molecules and the sequential ordered formation of up to eight new bonds (one C-O, two C-C, five C-N). The exclusive formation of six-membered heterocycles is elucidated by detailed modeling studies.

| S-EPMC7307965 | biostudies-literature

In Vitro Antiproliferative Evaluation of Synthetic Meroterpenes Inspired by Marine Natural Products.

Project description:Several marine natural linear prenylquinones/hydroquinones have been identified as anticancer and antimutagenic agents. Structure-activity relationship studies on natural compounds and their synthetic analogs demonstrated that these effects depend on the length of the prenyl side chain and on the type and position of the substituent groups in the quinone moiety. Aiming to broaden the knowledge of the underlying mechanism of the antiproliferative effect of these prenylated compounds, herein we report the synthesis of two quinones 4 and 5 and of their corresponding dioxothiazine fused quinones 6 and 7 inspired to the marine natural product aplidinone A (1), a geranylquinone featuring the 1,1-dioxo-1,4-thiazine ring isolated from the ascidian Aplidium conicum. The potential effects on viability and proliferation in three different human cancer cell lines, breast adenocarcinoma (MCF-7), pancreas adenocarcinoma (Bx-PC3) and bone osteosarcoma (MG-63), were investigated. The methoxylated geranylquinone 5 exerted the highest antiproliferative effect exhibiting a comparable toxicity in all three cell lines analyzed. Interestingly, a deeper investigation has highlighted a cytostatic effect of quinone 5 referable to a G0/G1 cell-cycle arrest in BxPC-3 cells after 24 h treatment.

| S-EPMC6950182 | biostudies-literature

Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds

Project description:The structural diversity

| S-EPMC9244947 | biostudies-literature

Iridium-catalyzed enantioconvergent hydrogenation of trisubstituted olefins.

Project description:Asymmetric hydrogenation of olefins constitutes a practical and efficient method to introduce chirality into prochiral substrates. However, the absolute majority of the developed methodologies is enantiodivergent and thus require isomerically pure olefins which is a considerable drawback since most olefination strategies produce (E/Z)-mixtures. Although some advances have been reported, a general enantioconvergent hydrogenation featuring a broad functional group tolerance remains elusive. Here, we report the development of a general iridium-catalyzed enantioconvergent hydrogenation of a broad range of functionalized trisubstituted olefins. The substitution pattern around the olefin is critical; whereas α-prochiral olefins can undergo an enantioconvergent hydrogenation, β-prochiral olefins react in an enantiodivergent manner. The presented methodology hydrogenates α-prochiral substrates with excellent control of enantioselection and high isolated yields. Most importantly, both isomerically pure alkenes as well as isomeric mixtures can be hydrogenated to yield the same major enantiomer in excellent enantiomeric excesses which is unusual in transition-metal catalyzed asymmetric hydrogenations.

| S-EPMC8766446 | biostudies-literature

I(III)-Catalyzed Oxidative Cyclization-Migration Tandem Reactions of Unactivated Anilines.

Project description:An I(III)-catalyzed oxidative cyclization-migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene or iodoalkane precatalyst suggests that the catalyst is present for the stereochemical determining C-N bond forming step.

| S-EPMC8135073 | biostudies-literature

Diastereo- and Enantioselective Syntheses of Trisubstituted Benzopyrans by Cascade Reactions Catalyzed by Monomeric and Polymeric Recoverable Bifunctional Thioureas and Squaramides.

Project description:4-Vinylphenyl-substituted squaramides have been tested as organocatalysts for the diastereo- and enantioselective synthesis of trisubstituted benzopyrans via an oxa-Michael intramolecular nitro-Michael cascade reaction. Both the enantio- and diastereoselection were good to moderate, depending on the nature of the chiral scaffold in the catalyst. The diastereoselection is better for the most active catalyst because the final products epimerize at C-3 along the time. Supported squaramide sq-9 prepared by copolymerization of sq-4 with styrene and divinylbenzene is also effective in promoting the cascade reaction, and it is recoverable and reusable for five cycles maintaining the activity.

| S-EPMC6644291 | 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