Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Stereoselective Synthesis of Cyclic Guanidines by Directed Diamination of Unactivated Alkenes.

ABSTRACT: A method for a directed stereoselective guanidinylation of alkenes is described. The guanidine unit can be delivered as an intact fragment by a hydroxy or carboxy group, usually with a high level of stereocontrol. After the guanidine delivery, the directing group can be cleaved under exceptionally mild conditions, typically by alcoholysis in the presence of acetic acid. Broad functional group tolerance and mild reaction conditions for the cycloguanidilation suggest applications in medicinal chemistry and natural products synthesis.

SUBMITTER: Mailyan AK

PROVIDER: S-EPMC5598158 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Stereoselective Synthesis of Cyclic Guanidines by Directed Diamination of Unactivated Alkenes.

Mailyan Artur K AK Young Kyle K Chen Joanna L JL Reid Bradley T BT Zakarian Armen A

Organic letters 20161025 21

A method for a directed stereoselective guanidinylation of alkenes is described. The guanidine unit can be delivered as an intact fragment by a hydroxy or carboxy group, usually with a high level of stereocontrol. After the guanidine delivery, the directing group can be cleaved under exceptionally mild conditions, typically by alcoholysis in the presence of acetic acid. Broad functional group tolerance and mild reaction conditions for the cycloguanidilation suggest applications in medicinal chem ...[more]

PMID: 27778502

Similar Datasets

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines.

Project description:A copper-catalyzed regio- and stereoselective diamination of unactivated alkenes has been developed with O-acylhydroxylamines as electrophilic nitrogen sources and oxidants. This method provides the first example of metal-catalyzed alkene diamination for directly installing an electron-rich amino group and extends the diamination scope for the synthesis of diverse 1,2-diamines. It offers a rapid and efficient approach to construct a wide range of 1,2-diamines that are an important structural motif in organic synthesis, medicines, catalysts and ligands.

| S-EPMC5707484 | biostudies-literature

Practical and stereoselective electrocatalytic 1,2-diamination of alkenes.

Project description:The 1,2-diamine motif is widely present in natural products, pharmaceutical compounds, and catalysts used in asymmetric synthesis. The simultaneous introduction of two amino groups across an alkene feedstock is an appealing yet challenging approach for the synthesis of 1,2-diamines, primarily due to the inhibitory effect of the diamine products to transition metal catalysts and the difficulty in controlling reaction diastereoselectivity and regioselectivity. Herein we report a scalable electrocatalytic 1,2-diamination reaction that can be used to convert stable, easily available aryl alkenes and sulfamides to 1,2-diamines with excellent diastereoselectivity. Monosubstituted sulfamides react in a regioselective manner to afford 1,2-diamines bearing different substituents on the two amino groups. The combination of an organic redox catalyst and electricity not only obviates the use of any transition metal catalyst and oxidizing reagent, but also ensures broad reaction compatibility with a variety of electronically and sterically diverse substrates.

| S-EPMC6823458 | biostudies-literature

Nickel-Catalyzed Stereoselective Arylboration of Unactivated Alkenes.

Project description:A Ni-catalyzed method for arylboration is disclosed. The method allows for highly stereoselective arylboration of unactivated alkenes. The reactions utilize a simple Ni-catalyst and work with a broad range of alkenes and aryl bromides. The products represent useful intermediates for chemical synthesis due to the versatility of the C-B bond. Preliminary mechanistic details of the method are also disclosed.

| S-EPMC5778876 | biostudies-literature

Rhodium(III)-Catalyzed Three-Component 1,2-Diamination of Unactivated Terminal Alkenes.

Project description:We report a three-component diamination of simple unactivated alkenes using an electrophilic nitrene source and amine nucleophiles. The reaction provides rapid access to 1,2-vicinal diamines from terminal alkenes through a one-pot protocol. The transformation proceeds smoothly with excellent tolerance for a broad array of primary and secondary amines, affording the desired product with good yield and regioselectivity. The mechanism is proposed to proceed through a Rh(III)-catalyzed aziridination of alkenes with subsequent ring opening by primary or secondary amines.

| S-EPMC8290961 | biostudies-literature

Pd-Catalyzed Alkene Diamination Reactions of Nitrogen Electrophiles: Synthesis of Cyclic Guanidines and Ureas Bearing Dialkylaminomethyl Groups.

Project description:The Pd-catalyzed coupling of N-allylguanidines or N-allylureas with O-benzoylhydroxylamine derivatives affords cyclic guanidines or cyclic ureas bearing dialkylaminomethyl groups. The desired products are obtained in good yield, and substrates bearing substituents at the allylic position are transformed with moderate diastereoselectivity. The mechanism of these reactions appears to involve anti-aminopalladation of the alkene, followed by a rare sp3C-sp3N bond-forming reductive elimination from an alkylpalladium complex that contains ?-hydrogen atoms.

| S-EPMC6375693 | biostudies-literature

Hydroxyl-directed stereoselective diboration of alkenes.

Project description:An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.

| S-EPMC4091278 | biostudies-literature

Stereoselective Synthesis of Isoxazolidines via Copper-Catalyzed Alkene Diamination.

Project description:A convenient copper-catalyzed intramolecular/intermolecular alkene diamination reaction to synthesize 3-aminomethyl-functionalized isoxazolidines under mild reaction conditions and with generally high levels of diastereoselectivity was achieved. This reaction demonstrates that previously underutilized unsaturated carbamates are good [Cu]-catalyzed diamination substrates. Sulfonamides, anilines, benzamide, morpholine, and piperidine can serve as the external amine source. This relatively broad amine range is attributed to the mild reaction conditions. Reduction of the N-O bond could also be achieved, revealing the corresponding 3,4-diamino-1-alcohols efficiently.

| S-EPMC5944859 | biostudies-literature

Directed nickel-catalyzed regio- and diastereoselective arylamination of unactivated alkenes.

Project description:Few methods have been reported for intermolecular arylamination of alkenes, which could provide direct access to important arylethylamine scaffolds. Herein, we report an intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitates formation of stabilized 4-, 5- or 6-membered nickelacycles and enables the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol is compatible with broad substrate scope and high functional group tolerance. The utility of this method is further demonstrated by the site-selective modification of pharmaceutical agents.

| S-EPMC8560905 | biostudies-literature

Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines.

Project description:We disclose a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ-alkenylketimines with aryl halides and alkylzinc reagents. The reaction produces γ-C(sp3)-branched δ-arylketones with the construction of two new C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. Electron-deficient alkenes play crucial dual roles as ligands to stabilize reaction intermediates and to increase catalytic rates for the formation of C(sp3)-C(sp3) bonds. This alkene alkylarylation reaction is also effective for secondary alkylzinc reagents and internal alkenes, and proceeds with a complete regio- and stereocontrol, affording products with up to three contiguous all-carbon all-cis secondary stereocenters.

| S-EPMC10569404 | biostudies-literature

Synthesis of cyclic guanidines via Pd-catalyzed alkene carboamination.

Project description:A new approach to the synthesis of substituted 5-membered cyclic guanidines is described. Palladium-catalyzed alkene carboamination reactions between acyclic N-allyl guanidines and aryl or alkenyl halides provide these products in good yield. This method allows access to a number of different cyclic guanidine derivatives in only two steps from readily available allylic amines.

| S-EPMC3857308 | 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