Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 9(3), P. 764 - 770
Published: Dec. 20, 2021
The first enantioselective synthesis of axially chiral styrene-type allylamines through phosphoric acid mediated atroposelective reductive amination 1-enal substituted 2-naphthols is achieved.
Language: Английский
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Jan. 15, 2024
Abstract The construction of N–N axially chiral motifs is an important research topic, owing to their wide occurrence in natural products, pharmaceuticals and ligands. One efficient method the atroposelective dihydropyrimidin-4-one formation. We present herein a direct catalytic synthesis atropisomers with simultaneous creation contiguous axial central chirality by oxidative NHC ( N -heterocyclic carbenes) catalyzed (3 + 3) cycloaddition. Using our method, we are able synthesize structurally diverse pyrroles indoles vicinal or bearing 2,3-dihydropyrimidin-4-one moiety moderate good yields excellent enantioselectivities. Further synthetic transformations obtained derivative products demonstrated. reaction mechanism origin enantioselectivity understood through DFT calculations.
Language: Английский
Citations
29
ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13363 - 13373
Published: Oct. 19, 2021
Reactions involving allenyl ion intermediates have been widely applied in the synthesis of functionalized allenes, but reactions radicals less studied and limited successful examples realized mainly by transition metal catalysis. We herein demonstrate generation N-heterocyclic carbene (NHC) organocatalysis their applications three-component radical relay 1,4-alkylcarbonylation 1,3-enynes without participation. This strategy could accommodate a collection different alkyl precursors such as CF3I, halides, cycloketone oxime esters, aliphatic carboxylic acid derived redox-active enabling convenient pathway to access range synthetically challenging tetra-substituted ketones with high regioselectivity. The key success this protocol relied on Csp-C(O)sp2 radical–radical coupling NHC-bound ketyl radicals, constructing ketone motifs highly efficient reaction pathway.
Language: Английский
Citations
86
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)
Published: Oct. 31, 2022
Atropisomers bearing multiple stereogenic axes are of increasing importance to the field material science, pharmaceuticals, and catalysis. However, atroposelective construction multi-axis atropisomers remains rare challenging, due intrinsical difficulties in stereo-control axes. Herein, we demonstrate a single-step new class 1,2-diaxially chiral triaryl α-pyranones by an N-heterocyclic carbene organocatalytic asymmetric [3+3] annulation well-designed alkynyl acylazolium precursors enolizable sterically hindered 2-aryl ketones. The protocol features broad substrate scope (>50 examples), excellent (most cases >20 : 1 dr, up 99.5 0.5 er), potentially useful synthetic applications. success this reaction relies on rational design structurally matched partners careful selection catalytic system. DFT calculations have also been performed discover rationalize origin high stereoselectivity reaction.
Language: Английский
Citations
54
Organic Letters, Journal Year: 2022, Volume and Issue: 24(3), P. 944 - 948
Published: Jan. 20, 2022
A method of N-fluorocarboxamide-directed N-heterocyclic-carbene (NHC)-catalyzed benzylic C-H acylation with aldehydes via the hydrogen atom transfer strategy is disclosed. This transformation involves a sequence single-electron transfer, 1,5-hydrogen and radical cross-coupling steps. offers facile access to various highly functionalized ketones exhibits good chemical yields functional group tolerance.
Language: Английский
Citations
43
Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(4)
Published: Oct. 7, 2022
N-Heterocyclic carbene (NHC) catalysis is a by now consolidated organocatalytic platform for number of synthetic (asymmetric) transformations via diverse reaction modes/intermediates. In addition to the typical umpolung processes involving acyl anion/homoenolate equivalent species, implementation protocols under oxidative conditions greatly expands possibilities this methodology. Oxidative NHC-catalysis allows and oxygenative through specific manipulations Breslow-type species depending upon oxidant used (external or O
Language: Английский
Citations
39
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 2127 - 2133
Published: Jan. 25, 2024
N-Heterocyclic carbenes (NHCs) have emerged as powerful organocatalysts in controlling the stereoselectivities of reaction sites that are remote from catalyst-binding position. Meanwhile, construction a stereogenic center at δ-position through NHC catalysis remains an unmet goal. Herein, we report NHC-catalyzed enantioselective 1,6-conjugated addition formyl enynes with nucleophiles oxidative LUMO activation strategy. The enables efficient chirality control enyne substrates, providing access to high-value-added enantio-enriched pyrano[2,3-b]indole and pyrano[2,3-c]pyrazole derivatives. In addition, central-to-axial transfer oxidation our products was realized, enabling facile axially chiral pyrans.
Language: Английский
Citations
11
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 24, 2025
An N-heterocyclic carbene-catalyzed atroposelective [3 + 3] annulation of alkynyl acylazoliums with benzothiazole derivatives has been developed for the divergent synthesis axially chiral triaryl 2-pyranones and fused 2-pyridones. The regioselectivity this protocol depends on structure benzothiazoles three different nucleophilic centers. obtained frameworks represent a new class arylheterocycle atropisomers, which may be potentially useful in medicinal chemistry.
Language: Английский
Citations
1
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 28, 2025
The in situ-generated pyrrolin-3-ones serve as novel and versatile synthons, being employed intermediates for the efficient production of pyrrole-fused lactones with high yield excellent enantioselectivity. Herein, we introduce emerging rhodium oxidative N-heterocyclic carbene relay catalysis that enables a highly enantioselective cascade annulation between easily available 1,2,3-triazoles enals. In this proof-of-concept study, engage α,β-unsaturated acylazolium generated from enals via catalysis.
Language: Английский
Citations
1
Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5456 - 5461
Published: July 20, 2022
Chiral NHC-catalyzed kinetic resolution of N-aryl aminomaleimides allowing the synthesis C-N axially chiral via remote chirality control is presented. The catalytically generated α,β-unsaturated acylazoliums from 2-bromoenals underwent selective [3 + 3] annulation with one enantiomers maleimide to furnish fused-dihydropyridinone (bearing axial/central chirality, up 6:1 dr, >99:1 er) leaving enantioenriched opposite enantiomer (up er). Studies on bond rotation barrier and dependence temperature are also provided.
Language: Английский
Citations
32
Chemical Communications, Journal Year: 2023, Volume and Issue: 59(36), P. 5395 - 5398
Published: Jan. 1, 2023
The first N-heterocyclic carbene organocatalytic three-component radical relay trifunctionalization of unactivated alkenes through the combination remote 1,4-cyano migration and alkylacylation was reported. This protocol features mild reaction conditions, readily available materials, excellent regioselectivity, capability late-stage functionalization.
Language: Английский
Citations
21