Browse
Submit Data
Databases
API
Help

Dataset Information

33 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Nickel-Catalyzed Asymmetric Reductive Cross-Coupling To Access 1,1-Diarylalkanes.

ABSTRACT: An asymmetric Ni-catalyzed reductive cross-coupling of (hetero)aryl iodides and benzylic chlorides has been developed to prepare enantioenriched 1,1-diarylalkanes. As part of these studies, a new chiral bioxazoline ligand, 4-heptyl-BiOX (L1), was developed in order to obtain products in synthetically useful yield and enantioselectivity. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, indoles, and piperidines.

SUBMITTER: Poremba KE

PROVIDER: S-EPMC5851002 | biostudies-literature | 2017 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Nickel-Catalyzed Asymmetric Reductive Cross-Coupling To Access 1,1-Diarylalkanes.

Poremba Kelsey E KE Kadunce Nathaniel T NT Suzuki Naoyuki N Cherney Alan H AH Reisman Sarah E SE

Journal of the American Chemical Society 20170413 16

An asymmetric Ni-catalyzed reductive cross-coupling of (hetero)aryl iodides and benzylic chlorides has been developed to prepare enantioenriched 1,1-diarylalkanes. As part of these studies, a new chiral bioxazoline ligand, 4-heptyl-BiOX (L1), was developed in order to obtain products in synthetically useful yield and enantioselectivity. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, indoles, and piperidines. ...[more]

PMID: 28406620

Similar Datasets

Nickel-Catalyzed Asymmetric Reductive Cross-Coupling between Heteroaryl Iodides and ?-Chloronitriles.

Project description:A Ni-catalyzed asymmetric reductive cross-coupling of heteroaryl iodides and ?-chloronitriles has been developed. This method furnishes enantioenriched ?,?-disubstituted nitriles from simple organohalide building blocks. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, quinolines, thiophenes, and piperidines. The reaction proceeds under mild conditions at room temperature and precludes the need to pregenerate organometallic nucleophiles.

| S-EPMC5066588 | biostudies-literature

Nickel-catalyzed asymmetric reductive cross-coupling between vinyl and benzyl electrophiles.

Project description:A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and benzyl chlorides has been developed. This method provides direct access to enantioenriched products bearing aryl-substituted tertiary allylic stereogenic centers from simple, stable starting materials. A broad substrate scope is achieved under mild reaction conditions that preclude the pregeneration of organometallic reagents and the regioselectivity issues commonly associated with asymmetric allylic arylation.

| S-EPMC4210114 | biostudies-literature

Nickel-catalyzed asymmetric reductive cross-coupling of α-chloroesters with (hetero)aryl iodides.

Project description:An asymmetric reductive cross-coupling of α-chloroesters and (hetero)aryl iodides is reported. This nickel-catalyzed reaction proceeds with a chiral BiOX ligand under mild conditions, affording α-arylesters in good yields and enantioselectivities. The reaction is tolerant of a variety of functional groups, and the resulting products can be converted to pharmaceutically-relevant chiral building blocks. A multivariate linear regression model was developed to quantitatively relate the influence of the α-chloroester substrate and ligand on enantioselectivity.

| S-EPMC8188512 | biostudies-literature

Photochemical Asymmetric Nickel-Catalyzed Acyl Cross-Coupling.

Project description:Photochemical enantioselective nickel-catalyzed cross-coupling reactions are difficult to implement. We report a visible-light-mediated strategy that successfully couples symmetrical anhydrides and 4-alkyl dihydropyridines (DHPs) to afford enantioenriched ?-substituted ketones under mild conditions. The chemistry does not require exogenous photocatalysts. It is triggered by the direct excitation of DHPs, which act as a radical source and as a reductant, facilitating the turnover of the chiral catalytic nickel complex.

| S-EPMC6900114 | biostudies-literature

Nickel/bis(oxazoline)-catalyzed asymmetric Negishi arylations of racemic secondary benzylic electrophiles to generate enantioenriched 1,1-diarylalkanes.

Project description:A tertiary stereogenic center that bears two different aryl substituents is found in a variety of bioactive compounds, including medicines such as Zoloft and Detrol. We have developed an efficient method for the synthesis of enantioenriched 1,1-diarylalkanes from readily available racemic benzylic alcohols. Formation of a benzylic mesylate (which is not isolated), followed by treatment with an arylzinc reagent, LiI, and a chiral nickel/bis(oxazoline) catalyst, furnishes the Negishi cross-coupling product in high ee and good yield. A wide array of functional groups (e.g., an aryl iodide, a thiophene, and an N-Boc-indole) are compatible with the mild reaction conditions. This method has been applied to a gram-scale synthesis of a precursor to Zoloft.

| S-EPMC3869004 | biostudies-literature

Nickel-Catalyzed Asymmetric Domino Ring Opening/Cross-Coupling Reaction of Cyclobutanones via a Reductive Strategy.

Project description:Herein we demonstrate the successful application of reductive strategy in the asymmetric domino ring opening/cross-coupling reaction of prochiral cyclobutanones. Under the catalysis of a chiral nickel complex, various aryl iodide-tethered cyclobutanones were reacted with alkyl bromides as the electrophilic coupling partner, providing a variety of chiral indanones bearing a quaternary stereogenic center in highly enantioselective manner, which can be further converted to diverse benzene-fused cyclic compounds including indane, indene, dihydrocoumarin, and dihydroquinolinone. The preliminary mechanistic investigations support a mechanism involving Ni(I)-mediated enantiotopic C-C σ-bond activation of cyclobutanones as key elementary step in the catalytic cycle.

| S-EPMC7155205 | biostudies-literature

Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling.

Project description:An asymmetric Ni-catalyzed reductive cross-coupling has been developed to prepare enantioenriched allylic silanes. This enantioselective reductive alkenylation proceeds under mild conditions and exhibits good functional group tolerance. The chiral allylic silanes prepared here undergo a variety of stereospecific transformations, including intramolecular Hosomi-Sakurai reactions, to set vicinal stereogenic centers with excellent transfer of chirality.

| S-EPMC5851001 | biostudies-literature

Nickel-Catalyzed Asymmetric Kumada Cross-Coupling of Symmetric Cyclic Sulfates.

Project description:Nickel-catalyzed enantioselective cross-couplings between symmetric cyclic sulfates and aromatic Grignard reagents are described. These reactions are effective with a broad range of substituted cyclic sulfates and deliver products with asymmetric tertiary carbon centers. Mechanistic experiments point to a stereoinvertive SN2-like oxidative addition of a nickel complex to the electrophilic substrate.

| S-EPMC5539537 | biostudies-literature

Stereospecific Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Tosylate and Allyl Alcohol Electrophiles.

Project description:The stereospecific cross-coupling of easily accessed electrophiles holds significant promise in the construction of C-C bonds. Herein, we report a nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates. This cross-coupling delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system consists of a simple nickel salt in conjunction with a commercially available reductant and importantly represents a rare example of a cross-coupling involving the C-O bonds of two electrophiles.

| S-EPMC8734645 | biostudies-literature

Nickel-catalyzed asymmetric reductive aryl-allylation of unactivated alkenes.

Project description:Herein we report a nickel-catalyzed asymmetric reductive aryl-allylation of aryl iodide-tethered unactivated alkenes, wherein both acyclic allyl carbonates and cyclic vinyl ethylene carbonates can serve as the coupling partners. Furthermore, the direct use of allylic alcohols as the electrophilic allyl source in this reaction is also viable in the presence of BOC anhydride. Remarkably, this reaction proceeds with high linear/branched-, E/Z- and enantio-selectivity, allowing the synthesis of various chiral indanes and dihydrobenzofurans (50 examples) containing a homoallyl-substituted quaternary stereocenter with high optical purity (90-98% ee). In this reductive reaction, the use of pregenerated organometallics can be circumvented, giving this process good functionality tolerance and high step-economy.

| S-EPMC8133004 | 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