Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Sequential C-O decarboxylative vinylation/C-H arylation of cyclic oxalates via a nickel-catalyzed multicomponent radical cascade.

ABSTRACT: A selective, sequential C-O decarboxylative vinylation/C-H arylation of cyclic alcohol derivatives enabled by visible-light photoredox/nickel dual catalysis is described. This protocol utilizes a multicomponent radical cascade process, i.e. decarboxylative vinylation/1,5-HAT/aryl cross-coupling, to achieve efficient, site-selective dual-functionalization of saturated cyclic hydrocarbons in one single operation. This synergistic protocol provides straightforward access to sp³-enriched scaffolds and an alternative retrosynthetic disconnection to diversely functionalized saturated ring systems from the simple starting materials.

SUBMITTER: Li H

PROVIDER: S-EPMC8159219 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Sequential C-O decarboxylative vinylation/C-H arylation of cyclic oxalates via a nickel-catalyzed multicomponent radical cascade.

Li Huan H Guo Lei L Feng Xiaoliang X Huo Liping L Zhu Shengqing S Chu Lingling L

Chemical science 20200414 19

A selective, sequential C-O decarboxylative vinylation/C-H arylation of cyclic alcohol derivatives enabled by visible-light photoredox/nickel dual catalysis is described. This protocol utilizes a multicomponent radical cascade process, i.e. decarboxylative vinylation/1,5-HAT/aryl cross-coupling, to achieve efficient, site-selective dual-functionalization of saturated cyclic hydrocarbons in one single operation. This synergistic protocol provides straightforward access to sp3-en ...[more]

PMID: 34122946

Similar Datasets

Nickel-Catalyzed Decarboxylative Arylation of Azoles with Perfluoro- and Nitrobenzoates.

Project description:This manuscript describes a Ni-catalyzed method for the direct arylation of azoles using benzoates. Perfluorophenyl and 2-nitrobenzoates participate in these reactions to afford the corresponding products in modest to good yields. The efficiency of the arylations with perfluorobenzoates is highly dependent on both the degree and position of fluorine atoms in the benzoates.

| S-EPMC4606873 | biostudies-literature

A dual photoredox-nickel strategy for remote functionalization via iminyl radicals: radical ring-opening-arylation, -vinylation and -alkylation cascades.

Project description:A divergent strategy for the remote arylation, vinylation and alkylation of nitriles is described. These processes proceed through the photoredox generation of a cyclic iminyl radical and its following ring-opening reaction. The distal nitrile radical is then engaged in nickel-based catalytic cycles to form C-C bonds with aryl bromides, alkynes and alkyl bromides.

| S-EPMC7053659 | biostudies-literature

Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis.

Project description:An asymmetric decarboxylative Csp(3)-Csp(2) cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety of naturally abundant α-amino acids and readily available aryl halides into valuable chiral benzylic amines in high enantiomeric excess, thereby producing motifs found in pharmacologically active agents.

| S-EPMC4862596 | biostudies-literature

Nickel-Catalyzed Radical Migratory Coupling Enables C-2 Arylation of Carbohydrates.

Project description:Nickel catalysis offers exciting opportunities to address unmet challenges in organic synthesis. Herein we report the first nickel-catalyzed radical migratory cross-coupling reaction for the direct preparation of 2-aryl-2-deoxyglycosides from readily available 1-bromosugars and arylboronic acids. The reaction features a broad substrate scope and tolerates a wide range of functional groups and complex molecular architectures. Preliminary experimental and computational studies suggest a concerted 1,2-acyloxy rearrangement via a cyclic five-membered-ring transition state followed by nickel-catalyzed carbon-carbon bond formation. The novel reactivity provides an efficient route to valuable C-2-arylated carbohydrate mimics and building blocks, allows for new strategic bond disconnections, and expands the reactivity profile of nickel catalysis.

| S-EPMC8418146 | biostudies-literature

Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids.

Project description:The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners. This mild decarboxylative arylation can also be utilized to efficiently access medicinal agents, as demonstrated by the rapid synthesis of fenofibrate.

| S-EPMC4526169 | biostudies-literature

Photocatalytic Enantioselective Radical Cascade Multicomponent Minisci Reaction of β-Carbolines Using Diazo Compounds as Radical Precursors.

Project description:Here, a photocatalytic asymmetric multicomponent cascade Minisci reaction of β-carbolines with enamides and diazo compounds is reported, enabling an effective enantioselective radical C─H functionalization of β-carbolines with high yields and enantioselectivity (up to 83% yield and 95% ee). This enantioselective multicomponent Minisci protocol exhibits step economy, high chemo-/enantio-selective control, and good functional group tolerance, allowing access to a variety of valuable chiral β-carbolines. Notably, diazo compounds are suitable radical precursors in enantioselective cascade radical reactions. Moreover, the efficiency and practicality of this approach are demonstrated by the asymmetric synthesis of bioactive compounds and natural products.

| S-EPMC11220658 | biostudies-literature

PPh3/NaI driven photocatalytic decarboxylative radical cascade alkylarylation reaction of 2-isocyanobiaryls.

Project description:The first triphenylphosphine/sodium iodide driven photocatalytic decarboxylative cascade cyclization of 2-isocyano-biaryls with alkyl N-hydroxyphthalimide (NHP) esters was developed. This operationally simple protocol results in multiple carbon-carbon bond formation under transition metal free conditions, affording a novel and environmentally benign entry to producing 6-alkyl phenanthridines with moderate to good yields.

| S-EPMC9052874 | biostudies-literature

Enantioselective C-H Arylation and Vinylation of Cyclobutyl Carboxylic Amides.

Project description:Chiral mono-N-protected aminomethyl oxazoline (MPAO) ligands are found to promote enantioselective C-H arylation and vinylation of the cyclobutyl carboxylic acid derivatives via Pd(II)/Pd(IV) redox catalysis. This ligand scaffold overcame two important limitations of the previous MPAHA (mono-N-protected α-amino-O-methylhydroxamic acid) ligands-enabled asymmetric C-H activation/C-C coupling reactions of cyclic carboxylic amides through Pd(II)/Pd(0) catalysis: substrates containing α-hydrogen atoms are not compatible; vinylation has not been developed. Sequential C-H arylation and vinylation of cyclobutanes are also accomplished to construct three consecutive chiral centers on the crowded cyclobutane rings, rendering this reaction highly versatile for the preparation of chiral cyclobutanes.

| S-EPMC5844484 | biostudies-literature

On-Resin Photochemical Decarboxylative Arylation of Peptides.

Project description:Here we describe the application of photochemical decarboxylative arylation as a late-stage functionalization reaction for peptides. The reaction uses redox-active esters of aspartic acid and glutamic acid on the solid phase to provide analogues of aromatic amino acids. By using aryl bromides as arylation reagents, a wide variety of amino acids can be accessed without having to synthesize them individually in solution. The reaction is compatible with proteinogenic amino acids and was used to perform a structure-activity relationship study of a PRMT5 binding peptide.

| S-EPMC11019635 | 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