Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of (+)-CP-99,994 via Pd(0)-catalyzed asymmetric allylic and homoallylic C-H Diamination of terminal olefin.

ABSTRACT: This paper describes an asymmetric synthesis of the potent substance P receptor antagonist (+)-CP-99,994 from 4-phenyl-1-butene via Pd(0)-catalyzed asymmetric allylic and homoallylic C-H diamination.

SUBMITTER: Fu R

PROVIDER: S-EPMC2752905 | biostudies-literature | 2009 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of (+)-CP-99,994 via Pd(0)-catalyzed asymmetric allylic and homoallylic C-H Diamination of terminal olefin.

Fu Renzhong R Zhao Baoguo B Shi Yian Y

The Journal of organic chemistry 20091001 19

This paper describes an asymmetric synthesis of the potent substance P receptor antagonist (+)-CP-99,994 from 4-phenyl-1-butene via Pd(0)-catalyzed asymmetric allylic and homoallylic C-H diamination. ...[more]

PMID: 19778085

Similar Datasets

Catalytic asymmetric allylic and homoallylic diamination of terminal olefins via formal C-H activation.

Project description:This paper describes a catalytic asymmetric diamination process for terminal olefins at allylic and homoallylic carbons via formal C-H activation using di-tert-butyldiaziridinone as nitrogen source with a catalyst generated from Pd2(dba)3 and chiral phosphorus amidite ligand. A wide variety of readily available terminal olefins can be effectively diaminated in good yields with high regio-, diastereo-, and enantioselectivities.

| S-EPMC2776772 | biostudies-literature

Tungsten-catalyzed asymmetric epoxidation of allylic and homoallylic alcohols with hydrogen peroxide.

Project description:A simple, efficient, and environmentally friendly asymmetric epoxidation of primary, secondary, tertiary allylic, and homoallylic alcohols has been accomplished. This process was promoted by a tungsten-bishydroxamic acid complex at room temperature with the use of aqueous 30% H2O2 as oxidant, yielding the products in 84-98% ee.

| S-EPMC3985688 | biostudies-literature

Synthetic and mechanistic studies on Pd(0)-catalyzed diamination of conjugated dienes.

Project description:Various dienes and a triene can be regioselectively diaminated at the internal double bond with good yields and high diastereoselectivity using di-tert-butyldiaziridinone (5) as the nitrogen source and Pd(PPh(3))(4) (1-10 mol %) as the catalyst. Kinetic studies with (1)H NMR spectroscopy show that the diamination is first-order in total Pd catalyst and inverse first-order in PPh(3). For reactive dienes, such as 1-methoxybutadiene (6g) and alkyl 1,3-butadienes (6a, 6j), the diamination is first-order in di-tert-butyldiaziridinone (5) and zero-order in the olefin. For olefins with relatively low reactivity, such as (E)-1-phenylbutadiene (6b) and (3E,5E)-1,3,5-decatriene (6i), similar diamination rates were observed when 3.5 equiv of olefins were used. Pd(PPh(3))(2) is likely to be the active species for the insertion of Pd(0) into the N-N bond of di-tert-butyldiaziridinone (5) to form a four-membered Pd(II) complex (A), which can be detected by NMR spectroscopy. The olefin complex (B), formed from intermediate A via ligand exchange between the olefin substrate and the PPh(3), undergoes migratory insertion and reductive elimination to give the diamination product and regenerate the Pd(0) catalyst.

| S-EPMC2846102 | biostudies-literature

Pd(0)-catalyzed 1,1-diarylation of ethylene and allylic carbonates.

Project description:An efficient protocol for the one-step synthesis of biologically relevant 1,1-diarylalkanes has been described. This reaction introduces two different aryl groups across the terminal end of simple feedstock alkenes such as ethylene and allylic carbonates. The propensity to generate ?-benzylpalladium intermediates dictates the exclusive 1,1-regioselectivity observed in the product.

| S-EPMC3955058 | biostudies-literature

Cu(I)-catalyzed asymmetric diamination of conjugated dienes.

Project description:A Cu(I)-catalyzed asymmetric diamination for a variety of conjugated dienes and a triene with encouraging ee's has been effectively achieved using (R)-DTBM-SEGPHOS as a chiral ligand and di- tert-butyldiaziridinone as the nitrogen source.

| S-EPMC2659555 | biostudies-other

Si-Directed regiocontrol in asymmetric Pd-catalyzed allylic alkylations using C1-ammonium enolate nucleophiles.

Project description:Cooperative catalysis enables the direct enantioselective ?-allylation of linear prochiral esters using Si-substituted allyl electrophiles. The Si-substituent directs the regioselectivity of enantioselective bond formation and provides products containing synthetically versatile pentafluorophenyl ester and vinylsilane moieties. Critical to the efficacy of this process was the recognition that the ancillary ligand on palladium could be altered to prevent formation of a deleterious ether by-product, whilst retaining enantioselectivity through the Lewis base catalyst. Flexibility such as this is unique to cooperative catalysis events and provides efficient access to an array of enantioenriched products that are orthogonally functionalized and easily modified.

| S-EPMC6294469 | biostudies-literature

Total synthesis of enantiopure (+)-gamma-lycorane using highly efficient Pd-catalyzed asymmetric allylic alkylation.

Project description:[reaction: see text] A highly efficient short total synthesis of (+)-gamma-lycorane (>99% ee, 41% overall yield) was achieved by using the asymmetric allylic alkylation in the key step catalyzed by palladium complexes with novel chiral biphenol-based monodentate phosphoramidite ligands.

| S-EPMC2562274 | biostudies-literature

Palladium-catalyzed allylic cross-coupling reactions of primary and secondary homoallylic electrophiles.

Project description:The Pd(0)-catalyzed allylic cross-coupling of homoallylic tosylate substrates using boronic acids and pinacol esters is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (quinox) as a ligand and is performed at ambient temperature. The scope of the reaction is broad in terms of both the boronate transmetalating reagent and the substrate and includes secondary tosylates. Mechanistic studies support an alkene-mediated S(N)2-type stereoinvertive oxidative addition of unactivated primary and secondary alkyl tosylates.

| S-EPMC3412144 | biostudies-literature

Photoinduced Olefin Diamination with Alkylamines.

Project description:Vicinal diamines are ubiquitous materials in organic and medicinal chemistry. The direct coupling of olefins and amines would be an ideal approach to construct these motifs. However, alkene diamination remains a long-standing challenge in organic synthesis, especially when using two different amine components. We report a general strategy for the direct and selective assembly of vicinal 1,2-diamines using readily available olefin and amine building blocks. This mild and straightforward approach involves in situ formation and photoinduced activation of N-chloroamines to give aminium radicals that enable efficient alkene aminochlorination. Owing to the ambiphilic nature of the β-chloroamines produced, conversion into tetra-alkyl aziridinium ions was possible, thus enabling diamination by regioselective ring-opening with primary or secondary amines. This strategy streamlines the preparation of vicinal diamines from multistep sequences to a single chemical transformation.

| S-EPMC7497254 | biostudies-literature

Pd-catalyzed synthesis of allylic silanes from allylic ethers.

Project description:Allylic phenyl ethers serve as electrophiles toward Pd(0) en route to a variety of allylic silanes. The reactions can be run at room temperature in water as the only medium using micellar catalysis.

| S-EPMC2804976 | 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