Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis.

ABSTRACT: Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action of nickel and sodium decatungstate catalysis. A wealth of ketones with high levels of structural complexity was rapidly obtained via direct functionalization of C(sp²)/C(sp³)-H bonds in a modular manner. Furthermore, a regioselective late-stage modification of natural products showcased the practical utility of the strategy, generally featuring high resource economy and ample substrate scope.

SUBMITTER: Wang D

PROVIDER: S-EPMC9214884 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis.

Wang Dingyi D Ackermann Lutz L

Chemical science 20220530 24

Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action of nickel and sodium decatungstate catalysis. A wealth of ketones with high levels of structural complexity was rapidly obtained via direct functionalization of C(sp2)/C(sp3)-H bonds in a modular manner. Furthermore, a regioselective late-stage modification of na ...[more]

PMID: 35799820

Similar Datasets

Nickel-Catalyzed Three-Component 1,2-Carboacylation of Alkenes.

Project description:Ketones, prevalent in many biologically significant molecules, require the development of novel methods to synthesize these structures, which is a critical endeavor in organic synthesis. Transition metal catalysis has proven to be an effective method for synthesizing ketones. However, the scope of these substrates remains relatively limited, particularly due to their incompatibility with sensitive functional groups. Herein, we report a Ni-catalyzed three-component 1,2-carboacylation of alkenes, which activates secondary/tertiary alkyl bromides. This method offers significant advantages: simplicity of operation, ready availability of substrates, and broad substrate applicability. A series of experimental studies have helped clarify the key mechanistic pathways involved in this cascade reaction.

| S-EPMC11433782 | biostudies-literature

Photoinitiated Three-Component α-Perfluoroalkyl-β-heteroarylation of Unactivated Alkenes via Electron Catalysis.

Project description:A visible-light-initiated α-perfluoroalkyl-β-heteroarylation of various alkenes with perfluoroalkyl iodides and quinoxalin-2(1 H)-ones is presented. This three-component radical cascade reaction allows an efficient synthesis of a range of perfluoroalkyl containing quinoxalin-2(1 H)-one derivatives in moderate to excellent yields under mild conditions. Reactions proceed via acidic aminyl radicals that are readily deprotonated to give the corresponding radical anions able to sustain the radical chain as single electron transfer reducing reagents. Hence, the overall cascade classifies as an electron-catalyzed process.

| S-EPMC6326532 | biostudies-literature

Intermolecular selective carboacylation of alkenes via nickel-catalyzed reductive radical relay.

Project description:The development of catalytic carboacylation of simple olefins, which would enable the rapid construction of ketones with high levels of complexity and diversity, is very challenging. To date, the vast majority of alkene carboacylation reactions are typically restricted to single- and two-component methodologies. Here we describe a three-component carboacylation of alkenes via the merger of radical chemistry with nickel catalysis. This reaction manifold utilizes a radical relay strategy involving radical addition to an alkene followed by alkyl radical capture by an acyl-nickel complex to forge two vicinal C-C bonds under mild conditions. Excellent chemoselectivity and regioselectivity have been achieved by utilizing a pendant weakly chelating group. This versatile protocol allows for facile access to a wide range of important β-fluoroalkyl ketones from simple starting materials.

| S-EPMC6113317 | biostudies-literature

Three-Component Aminoarylation of Electron-Rich Alkenes by Merging Photoredox with Nickel Catalysis.

Project description:A three-component 1,2-aminoarylation of vinyl ethers, enamides, ene-carbamates and vinyl thioethers by synergistic photoredox and nickel catalysis is reported. 2,2,2-Trifluoroethoxy carbonyl protected α-amino-oxy acids are used as amidyl radical precursors. anti-Markovnikov addition of the amidyl radical to the alkene and Ni-mediated radical/transition metal cross over lead to the corresponding 1,2-aminoarylation product. The radical cascade, which can be conducted under practical and mild conditions, features high functional group tolerance and broad substrate scope. Stereoselective 1,2-aminoarylation is achieved using a L-(+)-lactic acid derived vinyl ether as the substrate, offering a novel route for the preparation of protected enantiopure α-arylated β-amino alcohols. In addition, 1,2-aminoacylation of vinyl ethers is achieved by using an acyl succinimide as the electrophile for the Ni-mediated radical coupling.

| S-EPMC8252614 | biostudies-literature

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis.

Project description:N-Heterocyclic carbene (NHC) catalysis has emerged as a versatile tool in modern synthetic chemistry. Further increasing the complexity, several processes have been introduced that proceed via dual catalysis, where the NHC organocatalyst operates in concert with a second catalytic moiety, significantly enlarging the reaction scope. In biological transformations, multiple catalysis is generally used to access complex natural products. Guided by that strategy, triple catalysis has been studied recently, where three different catalytic modes are merged in a single process. In this Communication, direct α-C-H acylation of various alkenes with aroyl fluorides using NHC, sulfinate, and photoredox cooperative triple catalysis is reported. The method allows the preparation of α-substituted vinyl ketones in moderate to high yields with excellent functional group tolerance. Mechanistic studies reveal that these cascades proceed through a sequential radical addition/coupling/elimination process. In contrast to known triple catalysis processes that operate via two sets of interwoven catalysis cycles, in the introduced process, all three cycles are interwoven.

| S-EPMC8033569 | biostudies-literature

Three-component three-bond forming cascade via palladium photoredox catalysis.

Project description:A highly modular radical cascade strategy based upon radical cyclisation/allylic substitution sequence between alkyl/aryl bromides, 1,3-dienes and nucleophiles ranging from sulfinates to amines, phenols and 1,3-dicarbonyls is described (>80 examples). Palladium phosphine complexes - which merge properties of photo- and cross coupling-catalysts - allow to forge three bonds with complete 1,4-selectivity and stereocontrol, delivering highly value added carbocyclic and heterocyclic motifs that can feature - inter alia - vicinal quaternary centers, free protic groups, gem-difluoro motifs and strained rings. Furthermore, a flow chemistry approach was for the first time applied in palladium-photocatalysed endeavors involving radicals.

| S-EPMC8179282 | biostudies-literature

Three-component enantioselective alkenylation of organophosphonates via nickel metallaphotoredox catalysis.

Project description:The development of efficient catalytic multicomponent reactions (MCRs) is highly sought-after in chemical synthesis. However, catalytic asymmetric MCRs, particularly involving radical species, remain largely underdeveloped due to the exceptionally high reactivity of open-shell radical species. Herein, we report a metallaphotoredox-catalyzed asymmetric three-component method to access a diverse array of enantio-enriched α-alkenyl phosphonates from readily available vinyl phosphonates, alkenyl halides, and alkyl trifluoroborates under mild conditions. This operationally simple and redox-neutral protocol exhibits broad substrate scope and excellent chemo-, regio-, stereo-, and enantioselectivity. Furthermore, by simple modification of the triplet energy of the photocatalyst employed, both enantio-enriched trans and cis α-alkenyl phosphonates can be divergently accessed. Detailed computational and experimental studies were undertaken to elucidate the mechanism and origin of the observed reactivity and selectivity, which support a radical cascade sequence with α-phosphonate controlling the trajectory of radical capture by a chiral tetrahedral alkenyl nickel(II) species in the enantioselectivity-determining step.

| S-EPMC11566131 | biostudies-literature

General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis.

Project description:A visible-light-promoted photoredox/nickel protocol for the enantioselective three-component carboarylation of alkenes with tertiary and secondary alkyltrifluoroborates and aryl bromides is described. This redox-neutral protocol allows for facile and divergent access to a wide array of enantioenriched β-alkyl-α-arylated carbonyls, phosphonates, and sulfones in high yields and excellent enantioselectivities from readily available starting materials. We also report a modular and enantioselective synthesis of flurbiprofen analogs and piragliatin lead compound to demonstrate synthetic utility. Experimental and computational mechanistic studies were performed to gain insights into the mechanism and origin of chemo- and enantioselectivity.

| S-EPMC8131407 | biostudies-literature

Three-Component Ni-Catalyzed Silylacylation of Alkenes.

Project description:A Ni-catalyzed silylacylation of alkenes is presented. The reaction combines alkenes, ClZnSiR3, and acid chlorides to provide rapid access to β-silyl ketones. Importantly, the method involves a [Ni]-SiR3 complex as a catalytic intermediate, which is rarely described for three-component alkene functionalization. Finally, the synthetic utility of the products is demonstrated, and the mechanistic details are described.

| S-EPMC9031101 | biostudies-literature

Cu-Catalyzed Three-Component Carboamination of Alkenes.

Project description:Copper-catalyzed intermolecular carboamination of alkenes with α-halocarbonyls and amines is presented with 42 examples. Electron rich, electron poor, and internal styrenes, as well as α-olefins, are functionalized with α-halocarbonyls and aryl or aliphatic amines. Mechanistic investigations suggest the reaction is proceeding through addition of a carbon-centered radical across an olefin followed by oxidation to form a 5-membered oxocarbenium intermediate and subsequent nucleophilic ring opening to forge the C-N bond.

| S-EPMC6092015 | biostudies-literature