Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photocatalytic three-component asymmetric sulfonylation via direct C(sp³)-H functionalization.

ABSTRACT: The direct and selective C(sp³)-H functionalization of cycloalkanes and alkanes is a highly useful process in organic synthesis owing to the low-cost starting materials, the high step and atom economy. Its application to asymmetric catalysis, however, has been scarcely explored. Herein, we disclose our effort toward this goal by incorporation of dual asymmetric photocatalysis by a chiral nickel catalyst and a commercially available organophotocatalyst with a radical relay strategy through sulfur dioxide insertion. Such design leads to the development of three-component asymmetric sulfonylation involving direct functionalization of cycloalkanes, alkanes, toluene derivatives or ethers. The photochemical reaction of a C(sp³)-H precursor, a SO₂ surrogate and a common α,β-unsaturated carbonyl compound proceeds smoothly under mild conditions, delivering a wide range of biologically interesting α-C chiral sulfones with high regio- and enantioselectivity (>50 examples, up to >50:1 rr and 95% ee). This method is applicable to late-stage functionalization of bioactive molecules, and provides an appealing access to enantioenriched compounds starting from the abundant hydrocarbon compounds.

SUBMITTER: Cao S

PROVIDER: S-EPMC8062459 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Rapid and Direct Photocatalytic C(sp3 )-H Acylation and Arylation in Flow.

Project description:Herein, we report a photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow. The method exploits the ability of the decatungstate anion to act as a hydrogen atom abstractor and produce nucleophilic carbon-centered radicals that are intercepted by a nickel catalyst to ultimately forge C(sp3 )-C(sp2 ) bonds. Owing to the intensified conditions in flow, the reaction time can be reduced from 12-48 hours to only 5-15 minutes. Finally, kinetic measurements highlight how the intensified conditions do not change the reaction mechanism but reliably speed up the overall process.

| S-EPMC8518495 | biostudies-literature

Asymmetric Injection in Organic Transistors via Direct SAM Functionalization of Source and Drain Electrodes.

Project description:The fabrication of organic optoelectronic devices integrating asymmetric electrodes enables optimal charge injection/extraction at each individual metal/semiconductor interface. This is key for applications in devices such as solar cells, light-emitting transistors, photodetectors, inverters, and sensors. Here, we describe a new method for the asymmetric functionalization of gold electrodes with different thiolated molecules as a viable route to obtain two electrodes with drastically different work function values. The process involves an ad hoc design of electrode geometry and the use of a polymeric mask to protect one electrode during the first functionalization step. Photoelectron yield ambient spectroscopy and X-ray photoelectron spectrometry were used to characterize the energetic properties and the composition of the asymmetrically functionalized electrodes. Finally, we used poly(3-hexylthiophene)-based organic thin-film transistors to show that the asymmetric electronic response stems from the different electronic structures of the functionalized electrodes.

| S-EPMC6641596 | biostudies-literature

The Three-Component Synthesis of 4-Sulfonyl-1,2,3-triazoles via a Sequential Aerobic Copper-Catalyzed Sulfonylation and Dimroth Cyclization.

Project description:4-Sulfonyl-1,2,3-triazole scaffolds possess promising bioactivities and applications as anion binders. However, these structures remain relatively unexplored and efficient synthetic procedures for their synthesis remain desirable. A practical room-temperature, aerobic copper-catalyzed three-component reaction of aromatic ketones, sodium sulfinates, and azides is reported. This procedure allows for facile access to 4-sulfonyl-1,5-disubstituted-1,2,3-triazoles in yields ranging from 34 to 89%. The reaction proceeds via a sequential aerobic copper(II)chloride-catalyzed oxidative sulfonylation and the Dimroth azide-enolate cycloaddition.

| S-EPMC7865689 | biostudies-literature

Palladium-Catalyzed Access to Benzocyclobutenone-Derived Ketonitrones via C(sp2)-H Functionalization.

Project description:The palladium-catalyzed C(sp2)-H functionalization of bromoaryl aldonitrones leading to benzocyclobutenone-derived ketonitrones is described. This method allows for the preparation of a wide range of strained, four-membered ketonitrones with broad functional group tolerance. Downstream transformations of the formed products were readily demonstrated, illustrating the synthetic utility of the obtained benzocyclobutenone-derived nitrones for the construction of polycyclic nitrogen-containing scaffolds.

| S-EPMC9278523 | biostudies-literature

The Dark Side of Isocyanides: Visible-Light Photocatalytic Activity in the Oxidative Functionalization of C(sp3)-H Bonds.

Project description:The possibility to harness aromatic isocyanides as visible-light photocatalysts in the α-amino C(sp3)-H functionalization is herein presented. Actually, the three-component cross-dehydrogenative coupling of aromatic tertiary amines with isocyanides and water leads to amide products under very mild conditions in high yields and with a good substrate scope. While the reaction with aromatic isocyanides proceeds upon direct photoexcitation, aliphatic isocyanides are able to form a photoactive electron-donor-acceptor complex with aromatic amines. Moreover, the use of a catalytic loading of an aromatic isocyanide promotes the oxidative coupling of N-phenyl-1,2,3,4-tetrahydroisoquinoline with an array of different (pro)nucleophiles in good to excellent yields, thus providing the proof-of-concept for the development of a new highly tunable class of organic visible-light photocatalysts.

| S-EPMC8689654 | biostudies-literature

Enzymatic assembly of carbon-carbon bonds via iron-catalysed sp3 C-H functionalization.

Project description:Although abundant in organic molecules, carbon-hydrogen (C-H) bonds are typically considered unreactive and unavailable for chemical manipulation. Recent advances in C-H functionalization technology have begun to transform this logic, while emphasizing the importance of and challenges associated with selective alkylation at a sp3 carbon1,2. Here we describe iron-based catalysts for the enantio-, regio- and chemoselective intermolecular alkylation of sp3 C-H bonds through carbene C-H insertion. The catalysts, derived from a cytochrome P450 enzyme in which the native cysteine axial ligand has been substituted for serine (cytochrome P411), are fully genetically encoded and produced in bacteria, where they can be tuned by directed evolution for activity and selectivity. That these proteins activate iron, the most abundant transition metal, to perform this chemistry provides a desirable alternative to noble-metal catalysts, which have dominated the field of C-H functionalization1,2. The laboratory-evolved enzymes functionalize diverse substrates containing benzylic, allylic or α-amino C-H bonds with high turnover and excellent selectivity. Furthermore, they have enabled the development of concise routes to several natural products. The use of the native iron-haem cofactor of these enzymes to mediate sp3 C-H alkylation suggests that diverse haem proteins could serve as potential catalysts for this abiological transformation, and will facilitate the development of new enzymatic C-H functionalization reactions for applications in chemistry and synthetic biology.

| S-EPMC6440214 | biostudies-literature

Asymmetric benzylic C(sp3)-H acylation via dual nickel and photoredox catalysis.

Project description:Asymmetric C(sp3)-H functionalization is a persistent challenge in organic synthesis. Here, we report an asymmetric benzylic C-H acylation of alkylarenes employing carboxylic acids as acyl surrogates for the synthesis of α-aryl ketones via nickel and photoredox dual catalysis. This mild yet straightforward protocol transforms a diverse array of feedstock carboxylic acids and simple alkyl benzenes into highly valuable α-aryl ketones with high enantioselectivities. The utility of this method is showcased in the gram-scale synthesis and late-stage modification of medicinally relevant molecules. Mechanistic studies suggest a photocatalytically generated bromine radical can perform benzylic C-H cleavage to activate alkylarenes as nucleophilic coupling partners which can then engage in a nickel-catalyzed asymmetric acyl cross-coupling reaction. This bromine-radical-mediated C-H activation strategy can be also applied to the enantioselective coupling of alkylarenes with chloroformate for the synthesis of chiral α-aryl esters.

| S-EPMC8192574 | biostudies-literature

Metal-free C(sp3)-H functionalization of sulfonamides via strain-release rearrangement.

Project description:With the increasing awareness of sustainable chemistry principles, the development of an efficient and mild strategy for C(sp3)-H bond activation of nitrogen-containing compounds without the utilization of any oxidant and metal is still highly desired and challenging. Herein, we present a metal-free reaction system that enables C-H bond functionalization of aliphatic sulfonamides using DABCO as a promoter under mild conditions, affording a series of α,β-unsaturated imines in good yields with high selectivities. This protocol tolerates a broad range of functionalities and can serve as a powerful synthetic tool for the late-stage modification of complex compounds. More importantly, control experiments and detailed DFT calculations suggest that this process involves [2 + 2] cyclization/ring-cleavage reorganization, which opens up a new platform for the establishment of other related reorganization reactions.

| S-EPMC8179522 | biostudies-literature

Resolving Oxygenation Pathways in Manganese-Catalyzed C(sp3)-H Functionalization via Radical and Cationic Intermediates.

Project description:The C(sp3)-H bond oxygenation of the cyclopropane-containing mechanistic probes 6-tert-butylspiro[2.5]octane and spiro[2.5]octane with hydrogen peroxide catalyzed by manganese complexes bearing aminopyridine tetradentate ligands has been studied. Mixtures of unrearranged and rearranged oxygenation products (alcohols, ketones, and esters) are obtained, suggesting the involvement of cationic intermediates and the contribution of different pathways following the initial hydrogen atom transfer-based C-H bond cleavage step. Despite such a complex mechanistic scenario, a judicious choice of the catalyst structure and reaction conditions (solvent, temperature, and carboxylic acid) could be employed to resolve these oxygenation pathways, leading, with the former substrate, to conditions where a single unrearranged or rearranged product is obtained in good isolated yield. Taken together, the work demonstrates an unprecedented ability to precisely direct the chemoselectivity of the C-H oxidation reaction, discriminating among multiple pathways. In addition, these results conclusively demonstrate that stereospecific C(sp3)-H oxidation can take place via a cationic intermediate and that this path can become exclusive in governing product formation, expanding the available toolbox of aliphatic C-H bond oxygenations. The implications of these findings are discussed in the framework of the development of synthetically useful C-H functionalization procedures and the associated mechanistic features.

| S-EPMC9052745 | biostudies-literature

Catalytic asymmetric allylation of aldehydes with alkenes through allylic C(sp3)-H functionalization mediated by organophotoredox and chiral chromium hybrid catalysis.

Project description:We describe a hybrid system that realizes cooperativity between an organophotoredox acridinium catalyst and a chiral chromium complex catalyst, thereby enabling unprecedented exploitation of unactivated hydrocarbon alkenes as precursors to chiral allylchromium nucleophiles for asymmetric allylation of aldehydes. The reaction proceeds under visible light irradiation at room temperature, affording the corresponding homoallylic alcohols with a diastereomeric ratio >20/1 and up to 99% ee. The addition of Mg(ClO4)2 markedly enhanced both the reactivity and enantioselectivity.

| S-EPMC6430092 | biostudies-literature