The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 11, 2024
A catalyst-free reductive radical-polar crossover cyclization with alkenes and sodium dithionite to construct densely functionalized cyclic sultines was described. The key the success of this practical protocol relies not only on a bifunctional role dithionite, that is, serving as radical initiator SO
Language: Английский
ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941
Published: Jan. 17, 2025
Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly
Language: Английский
Citations
3
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: April 2, 2025
We present an asymmetric intramolecular [2 + 2] photocycloaddition reaction enabled by a dual catalyst system involving DPZ as photosensitizer and chiral Sc(III) complex, leading to azaarene-functionalized 2-azabicyclo[2.2.1]hexanes (aza-BCHs). The approach efficiently preventing racemization during subsequent nitrogen-deletion skeletal editing of aza-BCHs yield 2-substituted bicyclo[1.1.1]pentanes (BCPs). method achieves high ee broad substrate scope, including the successful formation all-carbon quaternary stereocenters. Furthermore, activation simple azaarene substrates Lewis acids in photocatalysis highlights notable contribution this field.
Language: Английский
Citations
1
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: May 29, 2024
Abstract Photocatalysis through energy transfer has been investigated for the facilitation of [4 + 2] cycloaddition reactions. However, high reactivity radical species poses a challenging obstacle to achieving enantiocontrol with chiral catalysts, as no enantioselective examples have reported thus far. Here, we present development catalytic asymmetric dearomative photocycloaddition involving anthracene and its derivatives alkenylazaarenes. This accomplishment is achieved by utilizing cooperative photosensitizer Brønsted acid catalysis platform. Importantly, this process enables activation substrates from triplet DPZ, thereby initiating precise stereoselective sequential transformation. The significance our work highlighted synthesis diverse range pharmaceutical valuable cycloadducts incorporating attractive azaarenes, all obtained yields, ees, drs. broad substrate scope further underscored successful construction all-carbon quaternary stereocenters adjacent stereocenters.
Language: Английский
Citations
8
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: May 22, 2025
An energy-transfer-enabled photochemical strategy merges 1,4-nitrogen migration with Norrish-Yang-type epoxidation to achieve skeletal editing of molecular frameworks. This approach bypasses classical di-π-methane rearrangements, providing an oxidant-free and atom-economical route epoxides via controlled C-O diradical recombination. The protocol accommodates >40 diverse substrates, including arenes, heterocycles, bioactive motifs, enabling late-stage functionalization complex architectures. Scalability is demonstrated through gram-scale synthesis (84% yield) one-pot cascades. Mechanistic studies reveal a triplet energy-transfer pathway distinct from radical chain processes, nitrogen directing regioselective
Language: Английский
Citations
0
Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(2), P. 171 - 171
Published: Jan. 1, 2024
Language: Английский
Citations
2
Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 6, 2024
A multicomponent heterogeneous semiconductor photocatalytic sulfinylsulfonylation of alkenes with alkyl iodides and SO
Language: Английский
Citations
2
Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown
Published: July 14, 2024
A visible-light-initiated energy-transfer enabled radical cyclization for the divergent synthesis of polycyclic γ-sultine derivatives has been developed. The reaction provides an alternative and expeditious access to benzofused frameworks, analogues γ-lactones γ-sultones, features good functional group compatibility, mild conditions excellent diastereoselectivity. robustness application potential this method have also successfully displayed by two gram-scale reactions sultones. Mechanistic studies indicated transformations through a possible intramolecular homolytic substitution or hydrogen atom transfer process mainly.
Language: Английский
Citations
1
Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 406 - 410
Published: Dec. 20, 2023
A thermoinduced radical homolytic substitution cyclization of alkenyl tethered sulfinate esters was displayed under mild metal-free conditions, enabling the functionalization alkenes and leading to structurally diverse value-added sultine products. The process utilizes readily available substrates using inexpensive 5% benzoyl peroxide (BPO) as an initiator generate functionalized sultines with broad functional group tolerance in medium excellent yields a highly atom-economical manner. In addition, obtained could be further toward valuable sultone frameworks one pot. thermo-catalytic chain proposed based on mechanistic studies.
Language: Английский
Citations
2
ChemCatChem, Journal Year: 2024, Volume and Issue: 16(13)
Published: March 13, 2024
Abstract The increasing use of fluorine‐containing bioactive molecules necessitates efficient strategies for fluorinated group installation. Despite the impressive development photoinduced radical fluoroalkylation as a powerful tool introducing fluorine, persistent issues, including recyclability and reaction specificity homogeneous photocatalysts, still leave great room further advancement in sustainable general fashion. Herein, we report conceptually different approach toward multiple types fluoroalkylations by using recoverable versatile graphitic carbon nitride (g‐CN) nanosheets heterogeneous photocatalyst. This photocatalytic system enables diverse intermolecular alkenes with fluoroalkanesulfinates intramolecular fluoroalkyl migrations alkenyl triflates. Detailed characterizations mechanism studies substantiate stability this organic semiconductor crucial role photogenerated electron‐hole pairs.
Language: Английский
Citations
0
The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 11, 2024
A catalyst-free reductive radical-polar crossover cyclization with alkenes and sodium dithionite to construct densely functionalized cyclic sultines was described. The key the success of this practical protocol relies not only on a bifunctional role dithionite, that is, serving as radical initiator SO
Language: Английский
Citations
0