Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Desymmetrization of unactivated bis-alkenes via chiral Bronsted acid-catalysed hydroamination.

ABSTRACT: Although great success has been achieved in catalytic asymmetric hydroamination of unactivated alkenes using transition metal catalysis and organocatalysis, the development of catalytic desymmetrising hydroamination of such alkenes remains a tough challenge in terms of attaining a high level of stereocontrol over both remote sites and reaction centers at the same time. To address this problem, here we report a highly efficient and practical desymmetrising hydroamination of unactivated alkenes catalysed by chiral Brønsted acids with both high diastereoselectivity and enantioselectivity. This method features a remarkably broad alkene scope, ranging from mono-substituted and gem-/1,2-disubstituted to the challenging tri- and tetra-substituted alkenes, to provide access to a variety of diversely functionalized chiral pyrrolidines bearing two congested tertiary or quaternary stereocenters with excellent efficiency under mild and user-friendly synthetic conditions. The key to success is indirect activation of unactivated alkenes by chiral Brønsted acids via a concerted hydroamination mechanism.

SUBMITTER: Yu ZL

PROVIDER: S-EPMC8159283 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Bronsted acid-catalysed enantioselective construction of axially chiral arylquinazolinones.

Project description:The axially chiral arylquinazolinone acts as a privileged structural scaffold, which is present in a large number of natural products and biologically active compounds as well as in chiral ligands. However, a direct catalytic enantioselective approach to access optically pure arylquinazolinones has been underexplored. Here we show a general and efficient approach to access enantiomerically pure arylquinazolinones in one-pot fashion catalysed by chiral phosphoric acids. A variety of axially chiral arylquinazolinones were obtained in high yields with good to excellent enantioselectivities under mild condition. Furthermore, we disclosed a method for atroposelective synthesis of alkyl-substituted arylquinazolinones involving Brønsted acid-catalysed carbon-carbon bond cleavage strategy. Finally, the asymmetric total synthesis of eupolyphagin bearing a cyclic arylquinazolinone skeleton was accomplished with an overall yield of 32% in six steps by utilizing the aforementioned methodology.

| S-EPMC5454535 | biostudies-literature

Iron-Catalyzed Hydroamination and Hydroetherification of Unactivated Alkenes.

Project description:The hydrofunctionalization of alkenes, explored for over 100 years, offers the potential for a direct, atom-economical approach to value-added products. While thermodynamically favored, the kinetic barrier to such processes necessitates the use of catalysts to control selectivity and reactivity. Modern variants typically rely on noble metals that require different ligands for each class of hydrofunctionalization, thereby limiting generality. This Letter describes a general iron-based system that catalyzes the hydroamination and hydroetherification of simple unactivated olefins.

| S-EPMC6583794 | biostudies-literature

Ni-catalysed reductive arylalkylation of unactivated alkenes.

Project description:In this protocol Ni-catalysed reductive arylalkylation of unactivated alkenes tethered to aryl bromides with primary alkyl bromides has been accomplished, providing a new path to construct diverse benzene-fused carbo- and heterocyclic cores including indanes, tetrahydroisoquinolines, indolines and isochromanes. Notably, this new method circumvents the pregeneration of organometallics and demonstrates high tolerance to a wide range of functional groups. The preliminary mechanistic investigations suggest a reaction pathway with an intermediate reduction.

| S-EPMC6369408 | biostudies-other

Chiral Pentacarboxycyclopentadiene-Based Bronsted Acid-Catalyzed Enantioselective Desymmetrization of Meso-Epoxides by 2-Mercaptobenzothiazoles.

Project description:Enantioselective desymmetrization of meso-epoxides by 2-mercaptobenzothiazoles was realized by using the pentacarboxycyclopentadiene-based chiral Brønsted acid in combination of N-isopropylaniline as amine additive to give up to 90.5:9.5 er of the ring opening products.

| S-EPMC6644688 | biostudies-literature

Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines.

Project description:We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.

| S-EPMC7202396 | biostudies-literature

One-pot anti-Markovnikov hydroamination of unactivated alkenes by hydrozirconation and amination.

Project description:A one-pot anti-Markovnikov hydroamination of alkenes is reported. The synthesis of primary and secondary amines from unactivated olefins was accomplished in the presence of a variety of functional groups. Hydrozirconation, followed by amination with nitrogen electrophiles, provides exclusive anti-Markovnikov selectivity. Most products are isolated in high yields without the use of column chromatography.

| S-EPMC3800136 | biostudies-literature

Development of highly efficient platinum catalysts for hydroalkoxylation and hydroamination of unactivated alkenes.

Project description:Hydrofunctionalization, the direct addition of an X-H (e.g., X=O, N) bond across an alkene, is a desirable strategy to make heterocycles that are important structural components of naturally occurring molecules. Described here is the design and discovery of "donor-acceptor"-type platinum catalysts that are highly effective in both hydroalkoxylation and hydroamination of unactivated alkenes over a broad range of substrates under mild conditions. A number of alkene substitution patterns are accommodated, including tri-substituted, 1,1-disubstituted, (E)-disubstituted, (Z)-disubstituted and even mono-substituted double bonds. Detailed mechanistic investigations suggest a plausible pathway that includes an unexpected dissociation/re-association of the electron-deficient ligand to form an alkene-bound "donor-acceptor"-type intermediate. These mechanistic studies help understand the origins of the high reactivity exhibited by the catalytic system, and provide a foundation for the rational design of chiral catalysts towards asymmetric hydrofunctionalization reactions.

| S-EPMC8007598 | biostudies-literature

Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer.

Project description:Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Reaction outcomes are consistent with the intermediacy of an N-centered sulfonamidyl radical generated via proton-coupled electron transfer activation of the sulfonamide N-H bond. Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented.

| S-EPMC6247111 | biostudies-literature

Metal-free Regioselective Hydrochlorination of Unactivated Alkenes via a Combined Acid Catalytic System.

Project description:A combined acid HCl/DMPU-acetic acid catalytic system was used in the hydrochlorination of a wide range of unactivated alkenes. This hydrochlorination strategy is remarkably greener than previous reported methods in terms of high atom efficiency, no toxic waste generated and metal-free process. The higher efficiency, compared with other commercially available HCl reagents, was augmented by the good regioselectivity and functionality tolerance found. A stepwise mechanism for this hydrochlorination process was proposed based on kinetic studies.

| S-EPMC5937714 | biostudies-literature

Chiral Bronsted acid-catalyzed allylboration of aldehydes.

Project description:The catalytic enantioselective allylation of aldehydes is a long-standing problem of considerable interest to the chemical community. We disclose a new high-yielding and highly enantioselective chiral Brønsted acid-catalyzed allylboration of aldehydes. The reaction is shown to be highly general, with a broad substrate scope that covers aryl, heteroaryl, alpha,beta-unsaturated, and aliphatic aldehydes. The reaction conditions are also shown to be effective for the catalytic enantioselective crotylation of aldehydes. We believe that the high reactivity of the allylboronate is due to protonation of the boronate oxygen by the chiral phosphoric acid catalyst.

| S-EPMC2928988 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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