Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides DOI Creative Commons
Wei‐Yang Ma, Matteo Leone, Étienne Derat

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: June 18, 2024

Abstract The radical Truce–Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules which asymmetric processes remains rare. By employing readily available and non‐expensive chiral auxiliary, we developed highly efficient photocatalytic acyl alkyl of α‐substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as hydrogen atom–transfer photocatalyst, along with aldehydes or C−H containing precursors. rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 2 d.r.) auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in density functional theory (DFT) calculations provided insights stereochemistry‐determining step.

Language: Английский

Nickel-Catalyzed Asymmetric Homobenzylic Hydroamidation of Aryl Alkenes to Access Chiral β-Arylamides DOI
Xiang Lyu,

Eunmi Jeon,

Changhyeon Seo

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in synthesis β-(hetero)arylethylamides. By employing transposed NiH catalysis approach, this method facilitates formation key chiral nickel-amido intermediates, enabling insertion into alkenes to produce desired β-arylamide products with excellent enantioselectivity. The exhibits high functional group tolerance utilizes readily available starting materials vinylarenes react dioxazolone as robust amidating source. Notably, approach was successfully applied pharmaceutical compounds natural products, such Clobenzorex, Direx, Selegiline, Sacubitril, Cipargamin.

Language: Английский

Citations

3
Photoredox catalytic alkylarylation of alkynes with arylsulfonylacetate as bifunctional reagent DOI

Chonglong He,

Min Wang, Yulong Wang

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(6), P. 2022 - 2028

Published: March 7, 2024

Language: Английский

Citations

13
Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines DOI
Yixiang Shi,

Yin Yuan,

Jianhui Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17580 - 17586

Published: June 20, 2024

The application of sulfinamides has been witnessed in medicinal and agrochemistry with employment asymmetric transformations. However, methods for their catalytic synthesis have rarely explored. Herein, the enantioselective addition aryl boroxines to sulfinylamines via Cu catalyst newly developed Xuphos ligand were reported. A series chiral can be readily accessed one step. This protocol enables stereospecific transformation sulfonimidoyl fluorides, sulfonimidamides, sulfonimidate esters. DFT calculations revealed reaction pathway, migratory insertion is enantio-determining noncovalent interaction between oxygen atom C-H bonds crucial enantioselectivity control.

Language: Английский

Citations

10
Total Synthesis of Dixiamycins A and B via a Late-Stage N–N Bond Formation under Visible Light Photoredox Catalysis DOI
Rhituparna Nandi, Ranjit Murmu, S. Sadhukhan

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(6), P. 1531 - 1536

Published: Jan. 30, 2025

Intermolecular oxidative N-N bond formation reactions are quite challenging and largely uncharted. linked dimeric indolosesquiterpene alkaloids represent an underexplored class of natural products, strategies for direct dehydrogenative limited. Here, we have reported that a late-stage visible-light photoredox catalysis facilitates formation, leading to the total syntheses atropo-diastereomers dixiamycins A (1a) B (1b).

Language: Английский

Citations

2
Asymmetric 2,3-Addition of Sulfinylamines with Arylboronic Acids Enabled by Nickel Catalysis DOI
Longlong Xi,

Xiaowu Fang,

Minyan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17587 - 17594

Published: June 24, 2024

Sulfinamides have been widely used in organic synthesis, with research on their preparation spanning more than a century. Despite advancements catalytic methodologies, creating sulfur stereocenters within these molecules remains significant challenge. In this study, we present an effective and versatile method for synthesizing diverse range of S-chirogenic sulfinamides through asymmetric aryl addition to sulfinylamines. By utilizing nickel complex as catalyst, process exhibits impressive enantioselectivity can incorporate various arylboronic acids at the position. The resulting synthetic are stable highly adaptable, allowing conversion variety sulfur-containing compounds. Our study also incorporates detailed experimental computational studies elucidate reaction mechanism factors influencing enantioselectivity.

Language: Английский

Citations

9
Energy‐Transfer Enabled 1,4‐Aryl Migration DOI Open Access

Shu‐Ya Wen,

Junjie Chen,

Yu Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 5, 2024

Abstract Functional group translocation is undoubtedly a pivotal synthetic transformation in organic chemistry. Numerous types of reactions involving radical 1,2‐aryl or 1,4‐aryl migration via electron transfer mechanism have been extensively investigated. Nevertheless, energy‐transfer enabled 1,4‐arylation remains unknown. Herein we disclose that an unprecedented di‐π‐ethane rearrangement featuring facilitated by energy catalysis under visible light conditions. The newly developed mild protocol exhibits tolerance towards diverse functional groups and enables the multitude aromatic rings, encompassing both electron‐withdrawing electron‐rich groups. open‐shell strategy has also found successful application modification several drugs. Large‐scale experiments, continuous‐flow experiment, versatile manipulation products demonstrated robustness potential utility this method. Preliminary mechanistic studies supported involvement species provided evidence for mechanism.

Language: Английский

Citations

9
Dialkylation of CF2 unit enabled by cobalt electron-shuttle catalysis DOI Creative Commons
Changqing Rao, Tianze Zhang, Hanmin Huang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 10, 2024

Language: Английский

Citations

7
Reductive sulfinylation by nucleophilic chain isomerization of sulfonylpyridinium DOI Creative Commons
Yifan Li, Weigang Zhang, Jeonguk Kweon

et al.

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

Published: Jan. 3, 2025

Language: Английский

Citations

1
Truce-smiles rearrangement mediated by ligand-to-iron charge transfer DOI Creative Commons

Fuyang Yue,

Ming‐Xing Li, Kangkang Yang

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 1, 2025

Language: Английский

Citations

1
Asymmetric reductive arylation and alkenylation to access S-chirogenic sulfinamides DOI Creative Commons

Xiaowu Fang,

Longlong Xi, Minyan Wang

et al.

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

Published: March 15, 2025

The study of the stereochemistry organic sulfur compounds has been ongoing for over a century, with S-chirogenic pharmacophores playing an essential role in drug discovery within bioscience and medicinal chemistry. Traditionally, synthesis sulfinamides featuring stereogenic sulfur(IV) centers involves complex, multistep process that often depends on chiral auxiliaries or kinetic resolution. Here, we introduce effective versatile method synthesizing diverse classes through selective aryl alkenyl addition to sulfinylamines. This is catalysed by nickel cobalt complex under reductive conditions, eliminating need preformed organometallic reagents. facilitates incorporation array halides at position, enabling their integration into various biologically significant pharmacophores. Our detailed mechanistic investigations density functional theory calculations provide insights reaction pathway, particularly highlighting enantiocontrol mode during process. play authors report methodology asymmetric sulfinylamines via common-Earth-metal catalysis.

Language: Английский

Citations

1