Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel-Catalyzed Transfer-Hydrogenative Strategy.

ABSTRACT: Nickel-catalyzed coupling of benzyl acrylates with activated ketones and imines provides ?-butyrolactones and lactams, respectively. The benzyl alcohol byproduct released during the lactonization/lactamization event is relayed to the next cycle where it serves as the reductant for C-C bond formation. This strategy represents a conceptually unique approach to transfer-hydrogenative C-C bond formation, thus providing examples of reductive heterocyclizations where hydrogen embedded within an alcohol leaving group facilitates turnover.

SUBMITTER: Buxton CS

PROVIDER: S-EPMC5656909 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel-Catalyzed Transfer-Hydrogenative Strategy.

Buxton Craig S CS Blakemore David C DC Bower John F JF

Angewandte Chemie (International ed. in English) 20171004 44

Nickel-catalyzed coupling of benzyl acrylates with activated ketones and imines provides γ-butyrolactones and lactams, respectively. The benzyl alcohol byproduct released during the lactonization/lactamization event is relayed to the next cycle where it serves as the reductant for C-C bond formation. This strategy represents a conceptually unique approach to transfer-hydrogenative C-C bond formation, thus providing examples of reductive heterocyclizations where hydrogen embedded within an alcoho ...[more]

PMID: 28868751

Similar Datasets

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

Reductive Arylation of Amides via a Nickel-Catalyzed Suzuki-Miyaura-Coupling and Transfer-Hydrogenation Cascade.

Project description:We report a means to achieve the addition of two disparate nucleophiles to the amide carbonyl carbon in a single operational step. Our method takes advantage of non-precious-metal catalysis and allows for the facile conversion of amides to chiral alcohols via a one-pot Suzuki-Miyaura cross-coupling/transfer-hydrogenation process. This study is anticipated to promote the development of new transformations that allow for the conversion of carboxylic acid derivatives to functional groups bearing stereogenic centers via cascade processes.

| S-EPMC7855255 | biostudies-literature

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

Project description: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.

| S-EPMC5851002 | 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 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

anti-Aminoallylation of aldehydes via ruthenium-catalyzed transfer hydrogenative coupling of sulfonamido allenes: 1,2-aminoalcohols.

Project description:Ruthenium-catalyzed transfer hydrogenation of N-sulfonamido allene 1e in the presence of aromatic aldehydes 2a-f, alpha,beta-unsaturated aldehydes 2g-i, and aliphatic aldehydes 2j-l results in reductive coupling to furnish the corresponding anti-aminoallylation products 3a-l. Reductive coupling of allenamide 1e to aldehyde 2a conducted using 2-propanol-d(8) as the terminal reductant delivers deuterio-3a. The observed pattern of deuterium incorporation suggests reversible allene hydrometalation with incomplete regioselectivity in advance of carbonyl addition. A survey of monosubstituted allenes 1f-i was conducted. High levels of anti-diastereoselectivity were observed only when tert-butyl allene 1f was used. This protocol represents an alternative to the use of amino-substituted allylborane reagents in carbonyl aminoallylation and avoids the use of stoichiometric metallic reagents.

| S-EPMC2676672 | biostudies-literature

Mechanism and transition-state structures for nickel-catalyzed reductive alkyne-aldehyde coupling reactions.

Project description:The mechanism of nickel-catalyzed reductive alkyne-aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d --> pi*(perpendicular) back-donation stabilizes the transition state and leads to higher reactivity for alkynes than alkenes. Strong Lewis acids accelerate the couplings with both alkynes and alkenes by coordinating with the aldehyde oxygen in the transition state.

| S-EPMC2824658 | 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

Ketones from Nickel-Catalyzed Decarboxylative, Non-Symmetric Cross-Electrophile Coupling of Carboxylic Acid Esters.

Project description:Synthesis of the C-C bonds of ketones relies upon one high-availability reagent (carboxylic acids) and one low-availability reagent (organometallic reagents or alkyl iodides). We demonstrate here a ketone synthesis that couples two different carboxylic acid esters, N-hydroxyphthalimide esters and S-2-pyridyl thioesters, to form aryl alkyl and dialkyl ketones in high yields. The keys to this approach are the use of a nickel catalyst with an electron-poor bipyridine or terpyridine ligand, a THF/DMA mixed solvent system, and ZnCl2 to enhance the reactivity of the NHP ester. The resulting reaction can be used to form ketones that have previously been difficult to access, such as hindered tertiary/tertiary ketones with strained rings and ketones with ?-heteroatoms. The conditions can be employed in the coupling of complex fragments, including a 20-mer peptide fragment analog of Exendin(9-39) on solid support.

| S-EPMC6707838 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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