Photocatalytic selective 1,4-oxyimination/diamination across C=C and N=N bonds to access structurally diverse N-N-N triazane derivatives DOI Creative Commons

Yu‐Shi Jiang,

Danna Chen, Huan Jiang

et al.

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

Strain-enabled radical spirocyclization cascades: rapid access to spirocyclobutyl lactones and – lactams DOI Creative Commons
Kousik Das,

Abhilash Pedada,

Tushar Singha

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(9), P. 3182 - 3191

Published: Dec. 21, 2023

Two complementary strain-enabled radical spirocyclization cascades have been realized to synthesize spirocyclobutyl lactones and – lactams. The reactions operate under mild conditions demonstrate excellent functional group compatibility.

Language: Английский

Citations

14
The Merger of Halogen Atom Transfer (XAT) and Energy Transfer Catalysis (EnT) for the Modular 1,2-Iminylalkylation of Diazenes DOI
Shanshan Li,

Yu‐Shi Jiang,

Li-Ning Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(38), P. 7009 - 7013

Published: Sept. 14, 2023

The 1,2-iminylalkylation of diazenes using alkyl iodides in combination with an O-benzoyl oxime is reported. In this transformation, acted as a radical precursor and XAT mediator. addition to common iodides, other such iodomethane, iodomethane-d3, trifluoroiodomethane, ethyl difluoroiodoacetate, iodoalkanes containing unprotected hydroxyl amide groups can also serve C-radical precursors the electrophilic acceptors.

Language: Английский

Citations

12
EnT‐Mediated Amino‐Sulfonylation of Alkenes with Bifunctional Sulfonamides: Access to β‐Amino Sulfone Derivatives DOI

Ji‐Wei Sang,

Peiyu Du,

Dingding Xia

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(43)

Published: May 23, 2023

Abstract β ‐Amino sulfones are commonly found structural motifs in biologically active compounds. Herein, we report a direct photocatalyzed amino‐sulfonylation reaction of alkenes for the efficicient production important compounds by simple hydrolysis without need additional oxidants and reductants. In this transformation, sulfonamides worked as bifunctional reagents, simultaneously generating sulfonyl radicals N ‐centered which were added to alkene highly atom‐economical fashion with high regioselectivity diastereoselectivity. This approach showed functional group tolerance compatibility, facilitating late‐stage modification some bioactive sulfonamide molecules, thereby expanding relevant chemical space. Scaling up led an efficient green synthesis apremilast, one best‐selling pharmceuticals, demonstrating synthetic utility applied method. Moreover, mechanistic investigations suggest that energy transfer (EnT) process was operation.

Language: Английский

Citations

11
Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: modular access to structurally complex α-amino ketones DOI Creative Commons
Jichao Xiao,

Tingting Jia,

Shuang Chen

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15489 - 15495

Published: Jan. 1, 2024

Nickel-catalyzed three-component reductive dicarbofunctionalization of activated olefins (enamides) is presented.

Language: Английский

Citations

4
Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling DOI Creative Commons
Guohui Zeng,

Dongwen Guo,

Huanfeng Jiang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

Citations

0
Development of N-centered radical scavengers that enables photoredox-catalyzed transition-metal-free radical amination of alkyl pinacol boronates DOI Creative Commons
Changlei Zhu, Jiaxin Lin, Xiaoguang Bao

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 4, 2025

In recent years, amination of alkylboronates through ionic copper catalysis or boron-ate complex 1,2-metalation has been well established, but complementary radical processes remain less studied before. Herein, based on rational design, we develop several imine-type N-centered scavengers and apply them to the alkylboronates. The reaction proceeds under mild photoredox-catalyzed transition-metal-free conditions features excellent functional group tolerance. It also enables preparation a range medicinally valuable amine derivatives from natural products. Further application this reagent in C-H amination, deoxygenative decarboxylative three component trifluoromethylative/sulfonylative aminations are realized. mechanistic studies DFT calculations conducted provide detailed evidence for mechanism.

Language: Английский

Citations

0
Cyclic Bifunctional Reagents Enabling a Strain-Release-Driven Formal [3 + 2] Cycloaddition of 2H-Azirines by Cascade Energy Transfer DOI Creative Commons
Alessia Petti,

Mathis J. Karrasch,

Preeti Chahar

et al.

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
Photocatalytic Multicomponent 1,n-Carboimination with Alkyl Iodides and O-Benzoyl Oxime through EnT and XAT Processes DOI

Xue-Ling Luo,

Miao-Sha Huang,

Shanshan Li

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6407 - 6412

Published: Aug. 21, 2023

In this study, we developed a strategy using commercially available alkyl iodides and O-benzoyl oxime to efficiently introduce iminyl groups via energy transfer halogen-atom processes. We performed three-component 1,2-carboimination of olefins four-component 1,4-carboimination across alkynes, resulting in the synthesis over 60 nitrogen-containing molecules. Moreover, transformation enables molecules with sensitive that were previously difficult achieve.

Language: Английский

Citations

10
Visible-Light-Mediated Two Transient C(sp3) Radical-Selective Cross-Coupling via Nickel Catalyst Continuous Capture: Synthesis of Pyrroline Derivatives DOI
Biao Yang, Xue‐Yang Wang,

Xie‐Tian Huang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15331 - 15339

Published: Nov. 13, 2023

Two C(sp3) radicals cross-coupling as a straightforward method for constructing C(sp3)–C(sp3) bonds has attracted extensive attention from chemists. Unfortunately, the strategy is challenging due to unexpected reactions of transient radicals, such homocoupling and hydrogen atom transfer. In this regard, capturing open-shell by metal catalysts can effectively enhance selectivity radical via formation more stable organometallic intermediates. Herein, we disclose selective two through dual combination iridium-catalyst-mediated decarboxylation nickel-catalyst-mediated continuous capture radicals. This mild atom-efficient Ni-catalyzed N-cyclization–alkylation protocol was employed prepare various alkyl–alkyl cross-coupled products. The synthetic applications methodology are demonstrated late-stage functionalization drugs, natural products, biomolecules.

Language: Английский

Citations

10
Synthesis of β-Silyl Amines via Merging Photoinduced Energy and Hydrogen Atom Transfer in Flow DOI
Yu Shao,

Cheng-jie Ying,

Yuan-Cui Wan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 30, 2024

The development of efficient methods for synthesizing β-silyl amines has long been a significant goal in organic synthesis. Previous mainly relied on the use prefunctionalized substrates or special reagents. Herein, we present visible-light-promoted synthesis approach amines, utilizing combination photoinduced energy and hydrogen atom transfer processes. Using flow chemistry technology, variety valuable skeletons, including α-amino esters, can be produced from readily available feedstocks such as hydrosilanes simple alkanes. Moreover, strategy's full-process fluidized production capability highlights its potential industrial-scale manufacturing. Mechanistic studies revealed that oxime esters act radical precursors well

Language: Английский

Citations

3