A crystalline doubly oxidized carbene

Nature, Journal Year: 2023, Volume and Issue: 623(7985), P. 66 - 70

Published: Sept. 20, 2023

Language: Английский

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1H-1,2,3-Triazol-5-ylidenes as Catalytic Organic Single-Electron Reductants

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2933 - 2938

Published: Jan. 22, 2024

Most of the known single-electron reductants are either metal based reagents, used in a stoichiometric amount, or combination an organic species and photocatalyst. Here we report that 1

Language: Английский

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Redox-Neutral Generation of Iminyl Radicals by N-Heterocyclic Carbene Catalysis: Rapid Access to Phenanthridines from Vinyl Azides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 5913 - 5917

Published: Aug. 4, 2022

An N-heterocyclic carbene-catalyzed oxidant-, metal- and light-free iminyl radical generation pathway stemming from the reaction of vinyl azide α-bromo ester is uncovered. This newly developed methodology successfully applied to redox-neutral construction a number diversified phenanthridine derivatives with nice functional group compatibility. Insights mechanism study reveal that this NHC-catalyzed transformation potentially proceeds through an alkyl addition-initiated HAS process, as active intermediate.

Language: Английский

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Divergent Construction of Heterocycles by SOMOphilic Isocyanide Insertion under N-Heterocyclic Carbene Catalysis

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7654 - 7658

Published: Oct. 11, 2022

A variety of phenanthridines are rapidly constructed by an N-heterocyclic carbene (NHC)-catalyzed SOMOphilic isocyanide insertion-initiated homolytic aromatic substitution-type radical cyclization in the absence any light, transition metals, and external oxidants. The aldehyde-free, scalable, operationally simple protocol tolerates diverse functionalized biaryl isonitriles activated α-halides. Moreover, it can be further applied to divergent construction other N-heterocycles. Preliminary mechanistic studies disclose that NHC-derived cation intermediate is possibly involved.

Language: Английский

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NHC-Catalyzed Regioselective Intramolecular Radical Cyclization Reaction for the Synthesis of Benzazepine Derivatives

Organic Letters, Journal Year: 2023, Volume and Issue: 25(32), P. 6072 - 6076

Published: Aug. 8, 2023

A novel and efficient strategy for the synthesis of a series structurally interesting benzazepine derivatives via an N-heterocyclic carbene-catalyzed regioselective intramolecular radical cyclization has been developed. This protocol features good regioselectivity, functional-group compatibility, wide substrate scope, providing transition-metal- oxidant-free pathway to access seven-membered rings under mild reaction conditions. Additionally, further transformation benzazepines large-scale experiment were also conducted.

Language: Английский

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Metal-Free Generation of γ-Cyanoalkyl Radicals by N-Heterocyclic Carbene Catalysis: Assembly of 6-Cyanoalkyl Phenanthridines

Organic Letters, Journal Year: 2022, Volume and Issue: 24(50), P. 9243 - 9247

Published: Dec. 14, 2022

A number of γ-cyanoalkyl radicals were generated by sustainable N-heterocyclic carbene catalysis in tin-, transition-meal-, and light-free conditions, followed insertion into biaryl isonitriles, thus leading to the rapid assembly a variety diversely functionalized 6-cyanoalkyl phenanthridines. preliminary mechanism study revealed that single-electron transfer radical process was possibly involved.

Language: Английский

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α‐Halocarbonyls as a Valuable Functionalized Tertiary Alkyl Source

ChemistryOpen, Journal Year: 2024, Volume and Issue: unknown

Published: July 11, 2024

Abstract This review introduces the synthetic organic chemical value of α‐bromocarbonyl compounds with tertiary carbons. compound a carbon has been used primarily only as radical initiator in atom transfer polymerization (ATRP) reactions. However, recent development photo‐radical reactions (around 2010), research on use alkyl precursors became popular 2012). As more examples were reported, studied not radicals but also for their applications organometallic and ionic That is, act nucleophiles well electrophiles. The carbonyl group is attractive because it allows skeleton to be converted after reaction, being applied total synthesis. In our survey until 2022, can perform full range necessary synthesis, including multi‐component reactions, cross‐coupling, substitution, cyclization, rearrangement, stereospecific asymmetric α‐Bromocarbonyl have created new trend alkylation, which then had limited reaction patterns focuses how chemistry.

Language: Английский

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Photoinduced Cerium‐Mediated Decarboxylative Alkylation Cascade Cyclization of N‐arylacrylamides and N‐acryl‐2‐aryl benzimidazoles

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(8)

Published: Feb. 28, 2023

Abstract A mild and versatile cerium‐mediated decarboxylative strategy for sequential alkylation/cyclization was developed the synthesis of quaternary oxindoles benzimidazo[2,1‐ a ]isoquinolin‐6(5 H )‐ones via photoinduced‐LMCT. This operationally simple procedure relies on inexpensive feedstock carboxylic acids as alkyl radical surrogates aerial molecular oxygen terminal oxidant. atom economical protocol showed viability with wide range (1° to 3° acids) coupling partners also allows late‐stage modification pharmaceutically‐important acids. Mechanistic studies revealed reaction follow pathway, while event studied by in situ FTIR.

Language: Английский

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Construction of all-carbon quaternary center by NHC-catalyzed Heck-type C–H tertiary alkylation

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100124 - 100124

Published: Feb. 1, 2025

Language: Английский

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1,2-Aminoalkylacylation of styrenes by cooperative NHC/photoredox dual catalysis

Synthetic Communications, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 9

Published: April 3, 2025

Language: Английский

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