Browse
Submit Data
Databases
API
Help

Dataset Information

37 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes.

ABSTRACT: A highly stereocontrolled syn-addition of silicon nucleophiles across cyclopropenes with two different geminal substituents at C3 is reported. Diastereomeric ratios are excellent throughout (d.r.≥98:2) and enantiomeric excesses usually higher than 90 %, even reaching 99 %. This copper-catalyzed C-Si bond formation closes the gap of the direct synthesis of α-chiral cyclopropylsilanes.

SUBMITTER: Zhang L

PROVIDER: S-EPMC6899982 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Diastereo- and enantioselective copper catalyzed hydroallylation of disubstituted cyclopropenes.

Project description:A highly diastereo- and enantioselective protocol for the hydroallylation of 1,1- and 1,2-disubstituted cyclopropenes has been developed utilizing an in situ formed copper hydride. A variety of allyl electrophiles could be utilized yielding a diverse range of trisubstituted cyclopropanes. Finally a preliminary enantioselective variant could be established employing a recently described P-stereogenic xantphos derivative as ligand.

| S-EPMC6115688 | biostudies-other

Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides.

Project description:Allylic gem-dichlorides are shown to be efficient substrates for catalytic asymmetric allylboration of alkynes. The method employs a chiral NHC-Cu catalyst capable of generating in a single step chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter with excellent levels of chemo-, regio- enantio- and diastereoselectivity. This high degree of functionalization makes these products versatile building blocks as illustrated with the synthesis of several optically active compounds. DFT calculations support the key presence of a metal cation bridge ligand-substrate interaction and account for the stereoselectivity outcome.

| S-EPMC9314970 | biostudies-literature

One-pot synthesis of GABA amides via the nucleophilic addition of amines to 3,3-disubstituted cyclopropenes.

Project description:A one-pot synthesis of various GABA amides has been demostrated, employing the nucleophilic addition of primary and secondary amines across the double bond of cyclopropene-3-carboxamides, followed by ring-opening of the resulting donor-acceptor cyclopropanes and subsequent in situ reduction of enamine (imine) intermediates.

| S-EPMC4749319 | biostudies-literature

Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones.

Project description:Enantioenriched alcohols found in an array of bioactive natural products and pharmaceutical agents are often synthesized by asymmetric nucleophilic addition to carbonyls. However, this approach generally shows limited functional-group compatibility, requiring the use of preformed organometallic reagents in conjunction with a stoichiometric or substoichiometric amount of chiral controller to deliver optically active alcohols. Herein we report a copper-catalyzed strategy for the stereoselective nucleophilic addition of propargylic and other alkyl groups to ketones, using easily accessible (poly)unsaturated hydrocarbons as latent carbanion equivalents. Our method features the catalytic generation of highly enantioenriched organocopper intermediates and their subsequent diastereoselective addition to ketones, allowing for the effective construction of highly substituted stereochemical dyads with excellent stereocontrol. Moreover, this process is general, scalable, and occurs at ambient temperature.

| S-EPMC5062742 | biostudies-literature

Enantio- and Diastereoselective Synthesis of Hydroxy Bis(boronates) via Cu-Catalyzed Tandem Borylation/1,2-Addition.

Project description:Catalytic enantioselective synthesis of 1-hydroxy-2,3-bisboronate esters through multicomponent borylation/1,2-addition is reported. Catalyst and substrates are readily available, form both a C-B and C-C bond, and generate up to three contiguous stereocenters. The reaction is tolerant of aryl, vinyl, and alkyl aldehydes and ketones in up to 95% yield, >20:1 dr, and 99:1 er. Intramolecular additions to aldehydes and ketones result in stereodivergent processes. The hydroxy bis(boronate) ester products are amenable to site-selective chemical elaboration.

| S-EPMC5837064 | biostudies-literature

Cobalt-Catalyzed Diastereoselective and Enantioselective Hydrosilylation of Achiral Cyclopropenes.

Project description:A mild diastereoselective and enantioselective cobalt-catalyzed hydrosilylation reaction of achiral cyclopropenes has been developed. In this protocol, various substituted cyclopropenes and arylsilanes were transformed, in the presence of readily available chiral cobalt complex, into silylcyclopropanes with high selectivities.

| S-EPMC7467819 | biostudies-literature

Palladium(II)-catalyzed enantio- and diastereoselective synthesis of pyrrolidine derivatives.

Project description:A palladium-catalyzed enantio- and diastereoselective synthesis of pyrrolidine derivatives is described. Initial intramolecular nucleopalladation of the tethered protected amine forms the pyrrolidine moiety and a quinone methide intermediate. A second nucleophile adds intermolecularly to afford diverse products in high enantio- and diastereoselectivity.

| S-EPMC3459323 | biostudies-literature

Enantio- and Diastereoselective, Lewis Base Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes.

Project description:A catalytic, enantio-, and diastereoselective formation of sulfenyl acetals bearing multiple stereogenic centers is reported. Alkenyl aldehydes undergo a chiral thiiranium ion initiated cascade starting with intramolecular capture by a formyl group and termination by capture with HFIP solvent. This method provides a one-pot synthesis of dihydropyran and 1,3-disubstituted isochroman acetals in good to excellent yield and with high levels of diastereo- (up to >99:1 dr) and enantiocontrol (up to 99:1 er).

| S-EPMC6713611 | biostudies-literature

Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines Enabled by Ligand-Controlled Chemoselective Hydrocupration.

Project description:The copper-catalyzed intermolecular enantioselective addition of styrenes to imines has been achieved under mild conditions at ambient temperature. This process features the use of styrenes as latent carbanion equivalents via the intermediacy of catalytically generated benzylcopper derivatives, providing an effective means for accessing highly enantiomerically enriched amines bearing contiguous stereocenters. Mechanistic studies shed light on the origin of the preferential styrene hydrocupration in the presence of an imine with the Ph-BPE-derived copper catalyst.

| S-EPMC5010012 | biostudies-literature

Iridium-Catalyzed Enantioselective and Diastereoselective Hydrogenation of 1,3-Disubstituted Isoquinolines.

Project description:The development of a general method utilizing a hydroxymethyl directing group for asymmetric hydrogenation of 1,3-disubstituted isoquinolines to provide chiral 1,2,3,4-tetrahydroisoquinolines is reported. The reaction, which utilizes [Ir(cod)Cl]2 and a commercially available chiral xyliphos ligand, proceeds in good yield with high levels of enantioselectivity and diastereo-selectivity (up to 95% ee and >20:1 dr) on a range of differentially substituted isoquinolines. Directing group studies demonstrate that the hydroxymethyl functional group at the C1-position is more efficient at enabling hydrogenation than other substituents, although high levels of enantioselectivity were conserved across a variety of polar and non-polar functional groups. By utilizing the generated chiral β-amino alcohol as a functional handle, the synthetic utility is further highlighted via the synthesis of 1,2-fused oxazolidine, oxazolidinone, and morpholinone tetrahydroisoquinolines in one step. Additionally, a non-natural analog of the tetrahydroprotoberberine alkaloids was successfully synthesized.

| S-EPMC8152574 | 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