Developing efficient and selective strategies to approach complex architectures containing (multi)stereogenic centers has been a long-standing synthetic challenge in both academia industry. Catalytic cascade reactions represent powerful means of rapidly leveraging molecular complexity from simple feedstocks. Unfortunately, carrying out Heck-type involving unactivated (tertiary) alkyl halides remains an unmet owing unavoidable β-hydride elimination. Herein, we show that modular, practical,...

The direct conversion of feedstock chemicals into value-added products is broad interest in chemical research. Herein, we present a regioselective and diastereoselective three-component dialkylation 1,3-dienes with Hantzsch esters aldehydes for the synthesis homoallylic alcohols. reaction enabled by dual photoredox chromium catalysis can also be performed enantioselectively employing chromium-bisoxazoline complexes.

The formation of carbon-carbon bonds lies at the heart synthetic organic chemistry and is widely applied to construct complex drugs, polymers, materials. Despite its importance, catalytic carbonyl arylation remains comparatively underdeveloped, due limited scope functional group tolerance. Herein we disclose an umpolung strategy achieve radical via dual catalysis. This redox-neutral approach provides a complementary method Grignard-type products from (hetero)aryl bromides aliphatic...

Molecular rearrangement occupies a pivotal position among fundamental transformations in synthetic chemistry. Radical translocation has emerged as prevalent tool, efficiently facilitating the migration of diverse functional groups. In contrast, development di-π-methane remains limited, particularly terms cyano This is primarily attributed to energetically unfavorable three-membered-ring transition state. Herein, we introduce an unprecedented di-π-ethane enabled by energy-transfer catalysis...

Open AccessCCS ChemistryRESEARCH ARTICLES9 Jan 2025Energy-Transfer-Enabled Rearrangement Involving Pyridines Shu-Ya Wen, Jun-Jie Chen, Yu Zheng and Huan-Ming Huang Wen School of Physical Science Technology, ShanghaiTech University, Shanghai 201210 , Chen *Corresponding author: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.024.202405071 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookXLinked InEmail The...

The carbonyl group stands as a fundamental scaffold and plays ubiquitous role in synthetically important chemical reactions both academic industrial contexts. Venerable transformations, including the aldol reaction, Grignard Wittig Nozaki-Hiyama-Kishi constitute vast empowering synthetic arsenal. Notwithstanding, two-electron mechanisms inherently confine breadth of accessible reactivity topological patterns.Fostered by rapid development photoredox catalysis, combing well-entrenched addition...

Abstract The rapid assembly of valuable cyclic amine architectures in a single step from simple precursors has been recognized as an ideal platform term efficiency and sustainability. Although vast number studies regarding synthesis reported, new synthetic disconnection approaches are still high demand. Herein, we report catalytic radical‐polar crossover cycloaddition to triggered primary sulfonamide under photoredox condition. This newly developed disconnection, comparable established...

We report a novel molecular iodine-catalyzed 1,3-dipolar cycloaddition/oxidation/aromatization cascade process with hydrogen peroxide as the terminal oxidant for construction of pyrrolo[2,1-a]isoquinolines. The product pyrrolo[2,1-a]isoquinolines were obtained from reactions between simple, readily available dipolarophiles and tetrahydroisoquinolines in moderate to excellent yields without need metal catalyst.

Radical-radical cyclization cascades, triggered by single-electron transfer to amide-type carbonyls SmI2-H2O, convert simple achiral barbiturates in one step hemiaminal- or enamine-containing tricyclic scaffolds containing up five contiguous stereocenters (including quaternary stereocenters). Furthermore, we describe the surprising beneficial effect of LiBr on most challenging radical-radical cascades. An alternative fragmentation-radical sequence related substrates allows access bicyclic...

Carbonyl propargylation has been established as a valuable tool in the realm of carbon-carbon bond forming reactions. The 1,3-enyne moiety recognized an alternative pronucleophile above transformation through ionic mechanism. Herein, we report for first time, radical carbonyl dual chromium/photoredox catalysis. A library homopropargylic alcohols bearing all-carbon quaternary centers could be obtained by catalytic three-component coupling 1,3-enynes, aldehydes and suitable precursors (41...

Highly selective dearomatizing radical cyclizations and cyclization cascades, triggered by single electron transfer to amide-type carbonyls SmI2-H2O-LiBr, provide efficient access unprecedented spirocyclic scaffolds containing up five stereocenters with high diastereocontrol. The first involving radicals derived from amide take place under mild conditions engage a range of aromatic heteroaromatic systems present in the barbiturate substrates. deliver new polycyclic hemiaminals or enamines...

Transforming C(sp3)–H bonds efficiently and selectively into C(sp3)–C(sp3) or C(sp3)–X is a highly relevant task. The direct arylation of allylic provides an elegant method for the formation unconjugated aryl-substituted olefins. Although both ionic- radical-based transition metal catalysis has been applied to achieve this transformation, numerous challenges remain. requirement persistent radical coupling partners, moderate selectivity need tri- tetrasubstituted olefins have limited...

Ketyl-olefin coupling reactions stand as one of the fundamental chemical transformations in synthetic chemistry and have been widely employed generation complex molecular architectures natural product synthesis. However, catalytic ketyl-olefin coupling, until recent development photoredox electrosynthesis through single-electron transfer mechanisms, has remained largely undeveloped. Herein, we describe a new approach to achieve by halogen-atom mechanism, which provides innovative efficient...

Abstract Herein, we report a modular photocatalytic platform for the site‐selective pyridination of saturated hydrocarbon compounds employing organic photoredox catalysis to forge new carbon‐carbon bonds. The C−H could couple benzylic/allylic bonds with pyridylphosphonium salts, which installed directly and regioselectively from heteroarenes through radical‐radical cross coupling mechanism. This synthetic methodology tolerate variety functional groups, complex heteroarenes, even late‐stage...

Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric reactions triggered by unstrained motifs remain rare. Herein, we report a mild and general strategy for activating diverse set of readily available alcohols the remote site-specific allylic alkylation ketones through combination photoredox-mediated proton-coupled electron transfer chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates...

Asymmetric multicomponent reactions that aim to control multiple chiral centers with high selectivity in a single step remain an on-gonging challenge. The realm of enantioselective radical-polar crossover transformation achieved through C-H Functionalization has yet be fully explored. Herein, we present successful description photoredox/Cr-catalyzed three-component (hetero)arylalkylation 1,3-dienes functionalization. A diverse array homoallylic alcohols could obtained good excellent yields,...