Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT

Chem, Journal Year: 2024, Volume and Issue: 10(10), P. 3088 - 3099

Published: June 19, 2024

Language: Английский

---

Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871

Published: Jan. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Language: Английский

---

Iron-catalyzed radical Markovnikov hydrohalogenation and hydroazidation of alkenes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 22, 2024

Abstract We herein report radical hydroazidation and hydrohalogenation of mono-, di- trisubstituted alkenes through iron catalysis. The alkene moiety that often occurs as a functionality in natural products is readily transformed into useful building blocks this approach. Commercially available tosylates α-halogenated esters are used trapping reagents combination with silanes reductants. reported Markovnikov hydroazidation, hydrobromination, hydrochlorination, hydroiodination occur under mild conditions. These hydrofunctionalizations valuable practical alternatives to ionic hydrohalogenations the corresponding mineral acids have be run harsher acidic conditions, which diminishes functional group tolerance. Good excellent diastereoselectivities can obtained for hydrofunctionalization cyclic alkenes.

Language: Английский

---

Cobalt/Photoredox Dual-Catalyzed Cross-Radical Coupling of Alkenes via Hydrogen Atom Transfer and Homolytic Substitution

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4893 - 4897

Published: June 5, 2024

Cobalt-catalyzed metal hydride hydrogen atom transfer (MHAT) in combination with photoredox catalysis has emerged as a powerful synthetic method, owing to its redox nature and applicability various radical precursors. Herein, we describe cross-radical coupling reaction under cobalt/photoredox dual catalysis. MHAT homolytic substitution (SH2) processes enabled Markovnikov-selective hydrobenzylation of di/trisubstituted alkenes, affording products quaternary carbon center redox-neutral manner.

Language: Английский

---

Harnessing Electro-Descriptors for Mechanistic and Machine Learning Analysis of Photocatalytic Organic Reactions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19019 - 19029

Published: July 4, 2024

Photocatalysis has emerged as an effective tool for addressing the contemporary challenges in organic synthesis. However, trial-and-error-based screening of feasible substrates and optimal reaction conditions remains time-consuming potentially expensive industrial practice. Here, we demonstrate electrochemical-based data-acquisition approach that derives a simple set redox-relevant electro-descriptors mechanistic analysis performance evaluation through machine learning (ML) photocatalytic These correlate to quantification shifted charge transfer processes response photoirradiation enabled construction reactivity diagram where high-yield reactive "hot zones" can reflect subtle changes system. For model deoxygenation reaction, influence varying carboxylic acids (substrate A, oxidation-intended) alkenes B, reduction-intended) on yield be visualized, while mathematical electro-descriptor patterns further revealed distinct mechanistic/kinetic impacts from different conditions. Additionally, application ML algorithms, experimentally derived overall redox kinetic outcome contributed vast parameters, serving capable means reduce dimensionality case complex multiparameter chemical space. As result, utilization efficient robust quantitative reactivity, demonstrating promising potential introducing operando-relevant experimental insights data-driven chemistry.

Language: Английский

---

Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Language: Английский

---

Cobalt-catalyzed enantioselective hydroetherification of alkenes and symmetric 1,3-diketones

Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101126 - 101126

Published: Oct. 1, 2024

Language: Английский

---

Formation of TEMPO Adducts with Hydrogen Atom Transfer: A New Pathway to Versatile Hydrofunctionalizations of Olefins

Published: Feb. 12, 2024

Since the seminal work by Mukaiyama, many research groups reported hydrofunctionalization of olefin with different metal hydrides in situ. Despite rapid development MHAT (metal-catalyzed hydrogen atom transfer)-derived reactions, need for using catalyst systems to accommodate reactivities makes it not appealing. Here, we describe a two-step process access broad range olefins. The first step involves cobalt-catalyzed formation TEMPO adduct from reaction demonstrates substrate scope and functional group tolerance. second photocatalytic nucleophilic addition generate new C-C, C-N, C-O, C-F, C-Cl bond. Interestingly our methodology, fluorination could be achieved short time, showing its potential PET applications. Combining two steps, net olefins can simply changing nucleophiles step. Noteworthily, diastereoselective hydration was also demonstrated employing bulkiness TEMPO.

Language: Английский

---

CoSalen-Catalyzed Radical Hydrofunctionalization of Unactivated Internal Olefins at Low Catalyst Loading: Method Development, Regioselectivity, and Applications in Post-Polymerization Modification

Published: Feb. 29, 2024

The past two decades witnessed the rapid development of CoSalen-catalyzed hydrofunctionalization reactions, mostly on terminal and conjugation-activated olefins. However, use 1,2-dialkylsubstituted alkenes continues to pose challenges. In this study, we revisit substrate class in context Carreira-type reactions introduce a simple yet effective modification (over 250-fold-increase TON). Near-quantitative yields can be achieved at low catalyst loading, typically 0.05 mol%. key lies inhibiting degradation Salen backbone using molecular sieves. This new protocol facilitates study MHAT regioselectivity type alkenes. We found that allylic electron-negative groups hyperconjugation have profound effects, yielding regioisomeric ratios ranging from 6.5:1 < 1:20. high TON, mild conditions, versatility method further enable its application post-polymerization several olefin-rich, commodity-relevant polymers.

Language: Английский

---

Dual‐Catalytic Structural Isomerisation as a Route to α‐Arylated Ketones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 9, 2024

Abstract Isomerisation reactions provide streamlined routes to organic compounds which are otherwise hard directly synthesise. The most common forms positional, geometrical or stereochemical isomerisations involve the relocation of a double bond change in relative location groups space. In contrast, far fewer examples structural (or constitutional) isomerisation exist where connectivity between atoms is altered. development platforms capable such rearrangement poses unique set challenges because chemical bonds must be selectively cleaved, and new ones formed without overall addition removal atoms. Here, we show that dual catalytic system can enable readily available allylic alcohols into more challenging‐to‐synthesise α‐arylated ketones via H‐atom transfer initiated semi‐pinacol rearrangement. Key our strategy combination cobalt catalyst photocatalyst under reductive, protic conditions allows intermediates propagate turnover. By providing an unusual disconnection motifs difficult access through direct arylation, anticipate inspiring other advanced strategies will further retrosynthetic logic for complex molecule synthesis.

Language: Английский

---