Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101200 - 101200
Published: Dec. 1, 2024
Language: Английский
Nature, Journal Year: 2025, Volume and Issue: 640(8057), P. 107 - 113
Published: April 2, 2025
Language: Английский
Citations
3
Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
The use of olefins in the construction cyclic compounds represents a powerful strategy for advancing pharmaceutical industry.
Language: Английский
Citations
2
Organic Letters, Journal Year: 2025, Volume and Issue: 27(5), P. 1244 - 1249
Published: Jan. 23, 2025
An asymmetric photoredox catalytic Minisci-type reaction between α-bromide amides and imine-containing azaarenes has been successfully developed. This catalyst system employs a chiral phosphoric acid alongside 3DPAFIPN as photosensitizer. The produces diverse array of valuable amides, featuring azaarene-substituted tertiary carbon stereocenters at the β-position, in high yields (up to 85%) good excellent enantioselectivities >99% enantiomeric excess (ee)). Importantly, this work marks first example radical addition simple utilizing radicals functionalized with electron-withdrawing carbonyl groups, which are conventionally considered unfavorable for such transformations, especially an enantioselective manner.
Language: Английский
Citations
1
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 29, 2025
Imine-containing azaarene-based triarylmethanes are vital molecular motifs that prevalent in a wide array of bioactive compounds. Recognizing the limitations current synthetic methodologies─marked by scarcity examples and difficulties flexible functional group modulation─we have developed an efficient modular asymmetric photochemical strategy employing pyridotriazoles boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles primary amines catalysts, we successfully synthesized diverse range with high yields excellent enantioselectivities. This method not only exhibits broad substrate scope outstanding tolerance but also enables precise synthesis deuterated derivatives using inexpensive D2O deuterium source. Mechanistic studies reveal unusual 1,4-boron shift is critical step generating boronated enamine intermediate, while shedding light on potential enantiocontrol mechanisms facilitated catalyst.
Language: Английский
Citations
1
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 18, 2024
Photochemical deracemization has emerged as one of the most straightforward approaches to access highly enantioenriched compounds in recent years. While excited-state events such energy transfer, single electron and ligand-to-metal charge transfer have been leveraged promote stereoablation, relying on hydrogen atom which circumvent limitations imposed by triplet redox potential racemic substrates, remain underexplored. Conceptually, attractive method for tertiary stereocenter might be abstraction followed donation. However, implementing a strategy poses significant challenges, primarily because products are also reactive if chiral catalyst is unable differentiate between two enantiomers. Herein we report distinct dual photochemical δ- γ-lactams, achieving high enantioenrichment deuterium incorporation despite inherent reactivity products. Mechanistic studies reveal that benzophenone enables nonselective while tetrapeptide-derived thiol dictates enantioselectivity donation step. More importantly, pyridine-based alcohol was found play crucial roles facilitating well enhancing
Language: Английский
Citations
6
Chemical Science, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
We report a cost-effective approach for the enantioselective hydrophosphinylation of ethynylazaarenes utilizing chiral copper catalytic platform. This strategy efficiently converts racemic secondary phosphine oxides (SPOs) into P-chiral tertiary (TPOs) bearing functionalized olefin substituents with azaarene moieties, achieving high yields and exceptional enantioselectivities. These adducts serve as crucial intermediates in development valuable 1,5-hybrid P,N-ligands. The facile introduction diverse additional carbon-centered chirality through transformation moiety effectively enhances enantioselectivity asymmetric metal catalysis compared to ligands exhibiting solely P-chirality. Mechanistic investigations reveal that interaction between Cu(i) complex azaarenes promotes kinetic resolution SPOs. robustness this method is further demonstrated by its ability incorporate deuterium atoms olefins, highlighting potential relevance pharmaceutical applications.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: April 14, 2025
Chiral spirocyclic oxetanes [2-oxo-spiro(3H-indole-3,2'-oxetanes)] were subjected to irradiation in the presence of a chiral thioxanthone catalyst (5 mol %) at λ = 398 nm. An efficient kinetic resolution was observed, which led an enrichment one oxetane enantiomer as major (15 examples, 37-50% yield, 93-99% ee). The minor underwent decomposition, and decomposition products carefully analyzed. They arise from photocycloreversion (retro-Paternò-Büchi reaction) into carbonyl component olefin. cycloreversion offers two cleavage pathways depending on whether C-O bond scission or C-C occurs carbon atom. course this reaction elucidated by suite mechanistic, spectroscopic, quantum chemical methods. In absence catalyst, exclusively initial scission, leading formaldehyde tetrasubstituted olefin products. Time-resolved spectroscopy femtosecond/picosecond time scale, synthetic experiments, calculations suggest occur first excited singlet state (S1). sensitizer, triplet states are populated, (T1) is responsible for isatin 1,1-diarylethene scission. explained recruiting predominantly oxindole. A two-point hydrogen-bonding interaction recognition enantiomer, corroborated NMR titration studies calculations. Transient absorption nanosecond/microsecond scale allowed observing quenching either enantiomers with slight preference enantiomer. competing situation both present, energy transfer suppressed initially better-binding and─as progresses─by oxindole fragmentation blocking binding site catalyst.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: April 17, 2025
Deracemization of C(sp3)-H arylated carbonyl compounds faces limitations in terms substrate scope. Through the photoactivation aryl group and stereocontrol generated arene radical cation via asymmetric ion-pairing catalysis, we are able to achieve deracemization at both enolizable unenolizable stereocenters. A diverse range α-, β-, γ-aryl ketones esters, including natural products medicinal derivatives, can be effectively converted into their enantiomers with high enantioselectivity. Mechanistic investigations through combined experimental computational studies suggest that reaction involves single-electron oxidation electron-rich groups, followed by a kinetic resolution resulting intermediates chiral phosphate anion. Deprotonation is identified as stereodetermining step, while stereoselective back electron transfer triplet-state quenching 3 Mes-Acr1+* may also affect enantioselectivity photostationary state.
Language: Английский
Citations
0
Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110758 - 110758
Published: Dec. 1, 2024
Language: Английский
Citations
1
Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101200 - 101200
Published: Dec. 1, 2024
Language: Английский
Citations
0