Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(36), P. 7316 - 7320
Published: Jan. 1, 2024
A facile and practical protocol to construct 2 H -imidazoles by applying an oxime acetate block as the sole component via homo/cross-coupling catalyzed Cu( i ) was developed.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10899 - 10907
Published: April 3, 2024
In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but ubiquitous biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access sparsely reported γ-amino directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across is made possible by intervention a radical Brook rearrangement takes place downstream EnT-mediated homolysis our reagent(s). combination experimental mechanistic investigations and detailed computational studies (DFT) indicates chain propagated reaction pathway.
Language: Английский
Citations
25
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
6
Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown
Published: Aug. 1, 2024
A highly selective and atom-economical multi-component remote difunctionalization strategy has been successfully developed. This utilizes precise control over the radical properties of bifunctional precursors electronic traits olefins diazenes to achieve effective radical-mediated 1,4-oxyimination/diamination across C=C N=N bonds. By capitalizing on compatibility reactivity tuning, this approach enables synthesis complex triazine compounds with an N-N-N framework, providing a versatile tool for constructing diverse molecular structures. metal-free method is atom-efficient adaptable various substrates, demonstrating remarkable tolerance broad range functional groups.
Language: Английский
Citations
3
Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110424 - 110424
Published: Sept. 1, 2024
Language: Английский
Citations
3
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: April 10, 2025
The energy transfer (EnT)-catalyzed ring opening and further decarboxylation of isoxazole-5(4H)-ones enables the in situ generation strained 2H-azirines. Subsequent selective C(sp2)-C(sp3) bond cleavage azirine intermediate allows a formal [3 + 2] cycloaddition with wide range electrophiles, unlocking access to valuable pyrroline-type moieties. Mechanistic experiments combination density functional theory (DFT) calculations revealed unique nature EnT-cascade process for three-membered aza-cycle while providing insight into regio- diastereoselectivity annulation. This mild straightforward method ensures rapid construction highly substituted cyclic imines, which can be easily converted pyrrolidines, fused oxaziridines, biologically relevant β-amino acid precursors.
Language: Английский
Citations
0
Chemical Communications, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Sulfonamidyl radicals are generated via photoinduced EnT and applied for the diamination of alkenes (hetero)arenes.
Language: Английский
Citations
2
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)
Published: July 17, 2024
1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N-functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2-diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N-heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2-aminothiolation styrenes.
Language: Английский
Citations
2
The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13585 - 13594
Published: Sept. 11, 2024
Herein, we report a simple and versatile difluoromethylene-imide reaction in which series of olefins can undergo difluoromethylenimine under photocatalytic conditions through an energy transfer (EnT) process. The has mild wide range applicability. We successfully synthesized 27 molecules containing difluoromethylene units, featuring easily accessible starting materials operational simplicity.
Language: Английский
Citations
2
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Nov. 26, 2024
Language: Английский
Citations
1
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)
Published: July 17, 2024
Abstract 1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N‐functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2‐diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N ‐heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2‐aminothiolation styrenes.
Language: Английский
Citations
0