Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

CuH-Catalyzed Regioselective Intramolecular Hydroamination for the Synthesis of Alkyl-Substituted Chiral Aziridines.

ABSTRACT: This report details a general and enantioselective means for the synthesis of alkyl-substituted aziridines. This protocol offers a direct route for the synthesis of alkyl-substituted chiral aziridines from achiral starting materials. Readily accessed allylic hydroxylamine esters undergo copper hydride-catalyzed intramolecular hydroamination with a high degree of regio- and enantiocontrol to afford the aziridine products in good to excellent yields in highly enantioenriched form. The utility of the products derived from this method is further demonstrated through derivatization of the chiral aziridine products to obtain a diverse array of functionalized enantioenriched amines.

SUBMITTER: Wang H

PROVIDER: S-EPMC5656387 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

CuH-Catalyzed Regioselective Intramolecular Hydroamination for the Synthesis of Alkyl-Substituted Chiral Aziridines.

Wang Haoxuan H Yang Jeffrey C JC Buchwald Stephen L SL

Journal of the American Chemical Society 20170615 25

This report details a general and enantioselective means for the synthesis of alkyl-substituted aziridines. This protocol offers a direct route for the synthesis of alkyl-substituted chiral aziridines from achiral starting materials. Readily accessed allylic hydroxylamine esters undergo copper hydride-catalyzed intramolecular hydroamination with a high degree of regio- and enantiocontrol to afford the aziridine products in good to excellent yields in highly enantioenriched form. The utility of t ...[more]

PMID: 28594548

Similar Datasets

Enantio- and regioselective CuH-catalyzed hydroamination of alkenes.

Project description:A highly enantio- and regioselective copper-catalyzed hydroamination reaction of alkenes has been developed using diethoxymethylsilane and esters of hydroxylamines. The process tolerates a wide variety of substituted styrenes, including trans-, cis-, and ?,?-disubstituted styrenes, to yield ?-branched amines. In addition, aliphatic alkenes coupled to generate exclusively the anti-Markovnikov hydroamination products.

| S-EPMC3874865 | biostudies-literature

Chiral Indoline Synthesis Via Enantioselective Intramolecular Copper-Catalyzed Alkene Hydroamination.

Project description:An enantioselective copper-catalyzed hydroamination / cyclization of N-sulfonyl-2-allylanilines for the synthesis of chiral 2-methylindolines is reported. Chiral 2-methylindolines are important subunits in drugs and bioactive compounds. This method provides chiral N-sulfonyl-2-methyl indolines in up to 90% ee.

| S-EPMC3519432 | biostudies-literature

Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination.

Project description:The CuH-catalyzed hydroamination of alkenes and alkynes using a silane and an amine transfer reagent represents a simple strategy to access chiral amine products. We have recently reported methods to prepare chiral amines with high efficiency and stereoselectivity using this approach. However, the current technology is limited to the synthesis of trialkylamines from dialkylamine transfer reagents (R2NOBz). When monoalkylamine transfer reagents [RN(H)OBz] were used for the synthesis of chiral secondary amines, competitive, nonproductive consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a modified type of amine transfer reagent that addresses this limitation. This effort has enabled us to develop a CuH-catalyzed synthesis of chiral secondary amines using a variety of amine coupling partners, including those derived from amino acid esters, carbohydrates, and steroids. Mechanistic investigations indicated that the modified amine transfer reagents are less susceptible to direct reaction with CuH.

| S-EPMC4528777 | biostudies-literature

Synthesis of ?-substituted tryptamines by regioselective ring opening of aziridines.

Project description:Functionalized tryptamines are targets of interest for development as small molecule therapeutics. The ring opening of aziridines with indoles is a powerful method for tryptamine synthesis if site selectivity can be controlled. 4-Nitrobenzyl carbamate (PNZ)-protected aziridines undergo regioselective ring opening to produce ?-substituted tryptamines for a series of indoles. The PNZ-protected tryptamines can be further manipulated by PNZ removal under mild conditions.

| S-EPMC4930112 | biostudies-literature

Diastereo- and Enantioselective CuH-Catalyzed Hydroamination of Strained Trisubstituted Alkenes.

Project description:Amine-substituted cyclobutanes and cyclopropanes are important substructures in biologically active compounds. Moreover, many of the cycloalkane units bear multiple substituents and stereocenters. Therefore, synthetic methods that produce polysubstituted aminocyclobutanes and aminocyclopropanes in a highly diastereo- and enantioselective manner are of importance. Herein, we describe the diastereo- and enantioselective synthesis of various types of polysubstituted aminocyclobutanes and aminocyclopropanes through CuH-catalyzed hydroamination of 1-substituted cyclobutenes and cyclopropenes. These strained trisubstituted alkenes exhibit much higher reactivity compared to their unstrained analogues in the initial hydrocupration step of the reaction. Moreover, an interesting reversal of regioselectivity was observed in the hydroamination of 1-aryl-substituted cyclobutenes compared to the cyclopropene analogues. The origins of the enhanced reactivity of strained trisubstituted alkenes as well as the differences in the regio- and enantioselectivity between reactions with cyclobutenes and cyclopropenes were investigated computationally.

| S-EPMC7928433 | biostudies-literature

Enantioselective CuH-catalyzed anti-Markovnikov hydroamination of 1,1-disubstituted alkenes.

Project description:Enantioselective synthesis of β-chiral amines has been achieved via copper-catalyzed hydroamination of 1,1-disubstituted alkenes with hydroxylamine esters in the presence of a hydrosilane. This mild process affords a range of structurally diverse β-chiral amines, including β-deuterated amines, in excellent yields with high enantioselectivities. Furthermore, catalyst loading as low as 0.4 mol% could be employed to deliver product in undiminished yield and selectivity, demonstrating the practicality of this method for large-scale synthesis.

| S-EPMC4235366 | biostudies-literature

Enantioselective thiourea-catalyzed intramolecular cope-type hydroamination.

Project description:Catalysis of Cope-type rearrangements of bis-homoallylic hydroxylamines is demonstrated using chiral thiourea derivatives. This formal intramolecular hydroamination reaction provides access to highly enantioenriched ?-substituted pyrrolidine products and represents a complementary approach to metal-catalyzed methods.

| S-EPMC3689223 | biostudies-literature

A Dual CuH- and Pd-Catalyzed Stereoselective Synthesis of Highly Substituted 1,3-Dienes.

Project description:Conjugated dienes are versatile building blocks and prevalent substructures in synthetic chemistry. Herein, we report a method for the stereoselective hydroalkenylation of alkynes, utilizing readily available enol triflates. We leveraged an in situ-generated and geometrically pure vinyl-Cu(I) species to form the Z,Z- or Z,E-1,3-dienes in excellent stereoselectivity and yield. This approach allowed for the synthesis of highly substituted Z-dienes, including pentasubstituted 1,3-dienes, which are difficult to prepare by existing approaches.

| S-EPMC9212073 | biostudies-literature

Rhodium-catalyzed asymmetric intramolecular hydroamination of unactivated alkenes.

Project description: Not available

| S-EPMC3394429 | biostudies-literature

Synthesis of Cyclic Guanidines via Silver-Catalyzed Intramolecular Alkene Hydroamination Reactions of N-Allylguanidines.

Project description:The silver-catalyzed hydroamination of tosyl-protected N-allylguanidines is described. These reactions provide substituted cyclic guanidines in high yields. The reactions are amenable to the construction of quaternary stereocenters as well as both monocyclic and bicyclic guanidine products.

| S-EPMC4924592 | 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