Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Diverse saturated heterocycles from a hydroacylation/conjugate addition cascade.

ABSTRACT: Rhodium-catalyzed hydroacylation using alkynes substituted with pendant nucleophiles, delivers linear α,β-unsaturated enone intermediates with excellent regioselectivity. These adducts are used to construct a broad range of diversely substituted, saturated O-, N- and S-heterocycles in a one-pot process. Judicious choice of cyclisation conditions enabled isolation of O-heterocycles with high levels of diastereoselectivity. A variety of derivatisation reactions are also performed, generating functionalised hydroacylation products. This sequence serves as a general approach for the synthesis of fully saturated heterocycles.

SUBMITTER: Iwumene NUN

PROVIDER: S-EPMC8809418 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Diverse saturated heterocycles from a hydroacylation/conjugate addition cascade.

Iwumene Ndidi U N NUN Moseley Daniel F DF Pullin Robert D C RDC Willis Michael C MC

Chemical science 20220119 5

Rhodium-catalyzed hydroacylation using alkynes substituted with pendant nucleophiles, delivers linear α,β-unsaturated enone intermediates with excellent regioselectivity. These adducts are used to construct a broad range of diversely substituted, saturated O-, N- and S-heterocycles in a one-pot process. Judicious choice of cyclisation conditions enabled isolation of O-heterocycles with high levels of diastereoselectivity. A variety of derivatisation reactions are also performed, generating funct ...[more]

PMID: 35222935

Similar Datasets

Convergent Synthesis of Diverse Nitrogen Heterocycles via Rh(III)-Catalyzed C-H Conjugate Addition/Cyclization Reactions.

Project description:The development of Rh(III)-catalyzed C-H conjugate addition/cyclization reactions that provide access to synthetically useful fused bi- and tricyclic nitrogen heterocycles is reported. A broad scope of C-H functionalization substrates and electrophilic olefin coupling partners is effective, and depending on the nature of the directing group, cyclic imide, amide, or heteroaromatic products are obtained. An efficient synthesis of a pyrrolophenanthridine alkaloid natural product, oxoassoanine, highlights the utility of this method.

| S-EPMC4973575 | biostudies-literature

Synthesis of Saturated N‐Heterocycles via a Catalytic Hydrogenation Cascade

Project description:Abstract Saturated N‐heterocycles are prominent motifs found in various natural products and pharmaceuticals. Despite the increasing interest in this class of compounds, the synthesis of saturated bicyclic azacycles requires tedious multi‐step syntheses. Herein, we present a one‐pot protocol for the synthesis of octahydroindoles, decahydroquinolines, and octahydroindolizines through a cascade reaction.

| S-EPMC9796080 | biostudies-literature

A mild catalytic system for radical conjugate addition of nitrogen heterocycles.

Project description:The direct addition of pyridine and diazine units to electron-poor alkenes has been achieved via a redox radical mechanism that is enabled by limiting the effective concentration of the hydrogen-atom source. The described method is tolerant of acidic functional groups and is generally applicable to the union of a wide range of Michael acceptors and 6-membered heterocyclic halides.

| S-EPMC5412691 | biostudies-literature

Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Lactams: Enantioselective Construction of All-Carbon Quaternary Stereocenters in Saturated Nitrogen-Containing Heterocycles.

Project description:Stereogenic nitrogen-containing heterocycles are ubiquitous in natural products and pharmaceutical compounds, but methods for their enantioselective construction have remained elusive. We report a general method for the asymmetric conjugate addition of arylboronic acids to β-alkyl/aryl α,β-unsaturated lactams that affords chiral β,β-disubstituted lactams. The transformation is operationally simple and air- and moisture-tolerant and uses a commercially available (S)-t-Bu-PyOx ligand. The method is high-yielding (up to 95% yield) and enantioselective (up to 97% ee) for a wide range of arylboronic acids and α,β-unsaturated lactams, including those with different ring sizes.

| S-EPMC10496148 | biostudies-literature

A metal-free aromative cascade for the synthesis of diverse heterocycles.

Project description:A metal-free aromative cascade has been developed for the synthesis of diverse heterocycles from readily accessible hydroxy/aminochalcones and acid/alkyl halides. The cascade being by a base-mediated intramolecular aldol cyclization/dehydration sequence to provide a triene, which sets the stage for a 6π-electrocyclization/oxidative aromatization to access diverse heterocyclic scaffolds.

| S-EPMC7197863 | biostudies-literature

Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation-aryl boronic acid conjugate addition sequence.

Project description:We demonstrate that a single Rh(i) complex can promote two mechanistically distinct C-C bond-forming reactions - alkyne hydroacylation and aryl boronic acid conjugate addition - to deliver substituted ketone products from the controlled assembly of three readily available fragments. This is a rare example of a Rh(i)/Rh(iii) cycle and a redox neutral Rh(i) cycle being promoted by a single catalyst. The process is broad in scope, allowing significant variation of all three reaction components. Incorporation of an enantiomerically pure bis-phosphine ligand renders the process enantioselective. Superior levels of enantioselectivity (up to >99% ee) can be achieved from using a two catalyst system, whereby two Rh(i) complexes, one incorporating an achiral bis-phosphine ligand and the second a chiral diene ligand, are introduced at the start of the reaction sequence.

| S-EPMC5351800 | biostudies-literature

Photomediated ring contraction of saturated heterocycles.

Project description:Saturated heterocycles are found in numerous therapeutics and bioactive natural products and are abundant in many medicinal and agrochemical compound libraries. To access new chemical space and function, many methods for functionalization on the periphery of these structures have been developed. Comparatively fewer methods are known for restructuring their core framework. Herein, we describe a visible light-mediated ring contraction of α-acylated saturated heterocycles. This unconventional transformation is orthogonal to traditional ring contractions, challenging the paradigm for diversification of heterocycles including piperidine, morpholine, thiane, tetrahydropyran, and tetrahydroisoquinoline derivatives. The success of this Norrish type II variant rests on reactivity differences between photoreactive ketone groups in specific chemical environments. This strategy was applied to late-stage remodeling of pharmaceutical derivatives, peptides, and sugars.

| S-EPMC8627180 | biostudies-literature

Synthesis of Enantioenriched Indolines by a Conjugate Addition/Asymmetric Protonation/Aza-Prins Cascade Reaction.

Project description:A conjugate addition/asymmetric protonation/aza-Prins cascade reaction has been developed for the enantioselective synthesis of fused polycyclic indolines. A catalyst system generated from ZrCl4 and 3,3'-dibromo-BINOL enables the synthesis of a range of polycyclic indolines in good yields and with high enantioselectivity. A key finding is the use of TMSCl and 2,6-dibromophenol as a stoichiometric source of HCl to facilitate catalyst turnover. This transformation is the first in which a ZrCl4 ⋅BINOL complex serves as a chiral Lewis-acid-assisted Brønsted acid.

| S-EPMC4843768 | biostudies-literature

Synthesis of warfarin analogs: conjugate addition reactions of alkenyl-substituted N-heterocycles with 4-hydroxycoumarin and related substrates.

Project description:We have developed a procedure for the Michael addition of 4-hydroxycoumarins to vinyl-substituted N-heterocycles. The chemistry is also suitable for thiocoumarins and quinolinones. A mechanism is proposed involving nucleophilic attack at the vinyl-group of the protonated N-heterocycle.

| S-EPMC9900474 | biostudies-literature

One-Pot Synthesis of 3,4-Dihydrocoumarins via C-H Oxidation/Conjugate Addition/Cyclization Cascade Reaction.

Project description:The 3,4-dihydrocoumarin derivatives were obtained from 2-alkyl phenols and oxazolones via C-H oxidation and cyclization cascade in the presence of silver oxide (Ag2O) and p-toluenesulfonic acid as a Brønsted acid catalyst. This approach provides a one-pot strategy to synthesize the multisubstituted 3,4-dihydrocoumarins with moderate to high yields (64-81%) and excellent diastereoselectivity (>20:1).

| S-EPMC10574682 | 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