Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

One Amine-3?Tasks: Reductive Coupling of Imines with Olefins in Batch and Flow.

ABSTRACT: Owing to their wide range of biological properties, ?-aminobutyric acid derivatives (GABA) have been extensively studied and found noteworthy industrial applications. However, atom-economical and efficient processes for their production are scarce and would greatly benefit from further investigations. Herein, we demonstrate that an iridium-based photocatalyst promotes the direct reductive cross-coupling of imines with olefins upon irradiation with visible light to give GABA derivatives in good yields and selectivities. We also stress the enabling triple role of tributylamine additive in this process, discuss the advantages of strategies based on proton-coupled electron transfer (PCET) and demonstrate the scale-up of this reaction in continuous flow.

SUBMITTER: Lefebvre Q

PROVIDER: S-EPMC7027816 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

One Amine-3 Tasks: Reductive Coupling of Imines with Olefins in Batch and Flow.

Lefebvre Quentin Q Porta Riccardo R Millet Anthony A Jia Jiaqi J Rueping Magnus M

Chemistry (Weinheim an der Bergstrasse, Germany) 20200121 6

Owing to their wide range of biological properties, γ-aminobutyric acid derivatives (GABA) have been extensively studied and found noteworthy industrial applications. However, atom-economical and efficient processes for their production are scarce and would greatly benefit from further investigations. Herein, we demonstrate that an iridium-based photocatalyst promotes the direct reductive cross-coupling of imines with olefins upon irradiation with visible light to give GABA derivatives in good y ...[more]

PMID: 31777987

Similar Datasets

Tertiary amine synthesis via reductive coupling of amides with Grignard reagents.

Project description:A new iridium catalyzed reductive coupling reaction of Grignard reagents and tertiary amides affording functionalised tertiary amine products via an efficient and technically-simple one-pot, two-stage experimental protocol, is reported. The reaction - which can be carried out on gram-scale using as little as 1 mol% Vaska's complex [IrCl(CO)(PPh3)2] and TMDS as the terminal reductant for the initial reductive activation step - tolerates a broad range of tertiary amides from (hetero)aromatic to aliphatic (branched, unbranched and formyl) and a wide variety of alkyl (linear, branched), vinyl, alkynyl and (hetero)aryl Grignard reagents. The new methodology has been applied directly to bioactive molecule synthesis and the high chemoselectivity of the reductive coupling of amide has been exploited in late stage functionalization of drug molecules. This reductive functionalisation of tertiary amides provides a new and practical solution to tertiary amine synthesis.

| S-EPMC5676097 | biostudies-literature

Preparation of stereodefined homoallylic amines from the reductive cross-coupling of allylic alcohols with imines.

Project description:Regio-, diastereo-, and enantioselective coupling reactions between imines and allylic alcohols have been developed. These coupling reactions deliver complex homoallylic amine products through a convergent C-C bond forming process that does not proceed through intermediate allylic organometallic reagents. In general, convergent coupling, by exposure of an allylic alkoxide to a preformed Ti-imine complex, occurs with allylic transposition in a predictable and stereocontrolled manner. While simple diastereoselection in these reactions is high, delivering anti-products with ?20:1 selectivity, the organometallic transformation described is compatible with a diverse range of functionality and substrates (including aliphatic and aromatic imines, allylic silanes, trisubstituted alkenes, vinyl- and aryl halides, trifluoromethyl groups, thioethers, and aromatic heterocycles). Alkene geometry of the products is a complex function of the allylic alcohol structure and is consistent with a mechanistic proposal based on syn-carbometalation followed by syn-elimination by way of a boat-like transition state geometry. Single asymmetric coupling reactions provide a means to translate the stereochemical information of the allylic alcohol to the homoallylic amine or to control diastereoselection in the coupling reactions of achiral allylic alcohols with chiral imines. Double asymmetric coupling reactions are also described that afford a unique means to control stereoselection in these complex convergent coupling processes. Finally, empirical models are proposed that are consistent with the observed stereochemical course of these coupling reactions en route to chiral homoallylic amines possessing di- or trisubstituted alkenes and anti- or syn- relative stereochemistry at the allylic and homoallylic positions.

| S-EPMC2993781 | biostudies-literature

?-Selective Reductive Coupling of Alkenylpyridines with Aldehydes and Imines via Synergistic Lewis Acid/Photoredox Catalysis.

Project description:Umpolung (polarity reversal) strategies of aldehydes and imines have dramatically expanded the scope of carbonyl and iminyl chemistry by facilitating reactions with non-nucleophilic reagents. Herein, we report the first visible light photoredox-catalyzed ?-selective reductive coupling of alkenylpyridines with carbonyl or iminyl derivatives with the aid of a Lewis acid co-catalyst. Our process tolerates complex molecular scaffolds (e.g., sugar, natural product, and peptide derivatives) and is applicable to the preparation of compounds containing a broad range of heterocyclic moieties. Mechanistic investigations indicate that the key step involves single-electron-transfer reduction of aldehydes or imines followed by the addition of resulting ketyl or ?-aminoalkyl radicals to Lewis acid-activated alkenylpyridines.

| S-EPMC5623169 | biostudies-literature

Access to Chiral Diamine Derivatives through Stereoselective Cu-Catalyzed Reductive Coupling of Imines and Allenamides.

Project description:Chiral 1,2-diamino compounds are important building blocks in organic chemistry for biological applications and as asymmetric inducers in stereoselective synthesis that are challenging to prepare in a straightforward and stereoselective manner. Herein, we disclose a cost-effective and readily available Cu-catalyzed system for the reductive coupling of a chiral allenamide with N-alkyl substituted aldimines to access chiral 1,2-diamino synthons as single stereoisomers in high yields. The method shows broad reaction scope and high diastereoselectivity and can be easily scaled using standard Schlenk techniques. Mechanistic investigations by density functional theory calculations identified the mechanism and origin of stereoselectivity. In particular, the addition to the imine was shown to be reversible, which has implications toward development of catalyst-controlled stereoselective variants of the identified reductive coupling of imines and allenamides.

| S-EPMC8025098 | biostudies-literature

Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides.

Project description:(Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon-nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C-N coupling method provides general and step-economical access to aryl amines.

| S-EPMC4990657 | biostudies-literature

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process.

Project description:Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

| S-EPMC5052654 | biostudies-literature

Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines.

Project description:The preparation of heterobenzylic amines by a Ni-catalyzed reductive cross-coupling between heteroaryl imines and C(sp3 ) electrophiles is reported. This umpolung-type alkylation proceeds under mild conditions, avoids the pre-generation of organometallic reagents, and exhibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent Ni center. The resulting bis(2-imino)heterocycle⋅Ni complexes can engage in alkylation reactions with a variety of C(sp3 ) electrophiles, giving heterobenzylic amine products in good yields.

| S-EPMC9474666 | biostudies-literature

Iron-Catalyzed Reductive Coupling of Alkyl Iodides with Alkynes To Yield cis-Olefins: Mechanistic Insights from Computation.

Project description:In a recent study, a new procedure for Z-selective olefin synthesis by reductive coupling of alkyl iodides with terminal alkynes in the presence of iron salts is described. This transformation is representative of many newly developed synthetic routes through the involvement of multiple species and phases, which makes mechanistic insight hard to obtain. Here, we report computational work aimed at exploring the possible reaction pathways. DFT calculations lead to two suggested routes, one involving C-I reduction by metallic zinc and radical addition to the alkyne and the other involving addition of two reduced iron species to the alkyne bond followed by reductive elimination. Comparison to experimental results as well as kinetic modeling is used to discuss the likelihood of these and related mechanisms.

| S-EPMC6990637 | biostudies-literature

Aliphatic imines in titanium-mediated reductive cross-coupling: unique reactivity of Ti(O-i-Pr)4/n-BuLi.

Project description:A procedure for the coupling of aliphatic imines with allylic and allenic alkoxides is described. The success of these studies was enabled by a unique reactivity profile of Ti(IV) isopropoxide/n-BuLi compared to well-known Ti(IV) isopropoxide/RMgX systems.

| S-EPMC2818175 | biostudies-literature

Branch-selective reductive coupling of 2-vinyl pyridines and imines via rhodium catalyzed C-C bond forming hydrogenation.

Project description:Hydrogenation of 2-vinyl azines 1a-1e in the presence of N-arylsulfonyl imines 2a-2l at ambient temperature and pressure employing cationic rhodium catalysts ligated by tri-2-furylphosphine results in regioselective reductive coupling to furnish branched products of imine addition 3a-3v, which embody modest to high levels of syn-diastereoselectivity. Catalytic coupling of 6-bromo-2-vinylpyridine 1a to imine 2l under an atmosphere of elemental deuterium provides deuterio-3l, with deuterium exclusively at the former beta-position of the vinyl moiety. These data are consistent with a catalytic mechanism involving oxidative coupling of the vinyl azine and imine partners to furnish a cationic aza-rhodacyclopentane, which upon deuteriolytic cleavage releases the adduct and regenerates cationic rhodium(I) to close the catalytic cycle. These studies represent the first metal catalyzed reductive C-C couplings of vinyl azines.

| S-EPMC2844715 | 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