A Sulfur Monoxide Surrogate Designed for the Synthesis of Sulfoxides and Sulfinamides** DOI Creative Commons

David Austrup,

Fumito Saito

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(51)

Published: Nov. 8, 2023

Abstract Sulfur monoxide (SO) is a highly reactive species that cannot be isolated in bulk. However, SO can play pivotal role as fundamental building block organic synthesis. Reported herein the design and application of sulfinylhydrazine reagent an easily prepared sulfur surrogate. We show facile thermal transfer from this to dienes where reaction using mechanistic probe suggests generation singlet SO. Combined with Grignard reagents appropriate carbon or nitrogen electrophiles, serves effective “SO” donor enable one‐pot, three‐component synthesis sulfoxides sulfinamides.

Language: Английский

Ligand-Enabled Palladium(II)-Catalyzed γ-C(sp3)–H Arylation of Primary Aliphatic Amines DOI
Chen‐Hui Yuan, Lei Jiao

Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 29 - 34

Published: Dec. 21, 2023

The Pd(II)/sulfoxide-2-hydroxypyridine catalytic system shows promising activity in C–H activation chemistry. In this study, we showcase how solves the problem of native primary amine-directed γ-C(sp3)–H arylation. Primary amines with different complexities are compatible established methodology, and range applicable substrates can be expanded to include pyridine, oxime ether, pyridine N-oxide.

Language: Английский

Citations

8
Unveiling the Mechanistic Role of Chiral Palladacycles in Pd(II)‐Catalyzed Enantioselective C(sp3)−H Functionalization DOI
Chen‐Hui Yuan, Xiaoxia Wang,

Keyun Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 7, 2024

Palladium-catalyzed enantioselective C(sp

Language: Английский

Citations

2
Pd(II)-Catalyzed Desymmetrizing gem-Dimethyl C(sp3)–H Alkenylation/Aza-Wacker Cyclization Directed by PIP Auxiliary DOI

Le‐Song Wu,

Tao Zhou, Bing‐Feng Shi

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(21), P. 4457 - 4462

Published: May 22, 2024

Desymmetrization of

Language: Английский

Citations

2
Recent Developments on the Synthesis of Sulfoxides via Sulfenate Anions DOI
Fumito Saito

Synthesis, Journal Year: 2023, Volume and Issue: 56(02), P. 220 - 228

Published: Aug. 16, 2023

Abstract Since the early 2000s, novel synthetic methods for preparation of sulfoxides have emerged that involve sulfenate anions as sulfur nucleophiles. This short review showcases key advances in these protocols, including catalytic enantioselective alkylation and arylation, provides future directions this research field. 1 Introduction 2 Precursors Sulfenate Anions 3 Organocatalytic Enantioselective Alkylation 4 Palladium-Catalyzed Arylation 5 Coupling with Hypervalent Iodine Reagents 6 Conclusions Outlook

Language: Английский

Citations

4
Non‐Directed C−H Arylation of Anisole Derivatives via Pd/S,O‐Ligand Catalysis DOI Creative Commons

Kezuan Deng,

Verena Sukowski, M.A. Fernandez-Ibanez

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Feb. 24, 2024

Abstract Non‐directed C−H arylation is one of the most efficient methods to synthesize biaryl compounds without need prefuctionalization starting materials, or installment and removal directing groups on substrate. A direct simple arenes as limiting reactants remains a challenge. Here we disclose non‐directed anisole derivatives reagents with aryl iodides under mild reaction conditions. The arylated products are obtained in synthetically useful yields bioactive molecules also demonstrated. Key success this methodology use one‐step synthesized S,O‐ligand.

Language: Английский

Citations

1
Divergent Reaction of Alkynes and TsCN: Synthesis of β-Sulfinyl Alkenylsulfones and (E)-Vinyl Sulfones DOI

Guiting Peng,

Xin Yu, Jiang Bai

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12159 - 12169

Published: Aug. 16, 2024

An efficient and high-selectivity approach for the divergent synthesis of β-sulfinyl alkenylsulfones (E)-vinyl sulfones from alkynes TsCN is described. A series disulfurized products were constructed under mild conditions in absence transition metals. This transformation featured excellent regio- stereoselectivity, good functional group compatibility, broad substrate scope. The copper(I)-catalyzed sulfonation with that affords to yields was also developed.

Language: Английский

Citations

1
Palladium catalyzed ortho-C(sp2)–H activation/cyclization of aryl amines assisted by imine and vinylacetic acid DOI Creative Commons

Xiangwen Tan,

Yaru Jing, Jiahao Wu

et al.

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

Published: Nov. 14, 2024

Palladium-catalyzed directed C − H functionalization/cyclization is an effective approach for synthesizing nitrogen heterocycles. Imine, known its ease of installation/removal, has been extensively used in the C–H activation aldehydes, ketones, and alkylamines. Nevertheless, it rarely explored C(sp2)–H aryl amines because generation a strained four-membered palladacycle. Herein, imine palladium catalyzed functionalization assisted by vinylacetic acid established, providing access to variety γ-lactone fused tetrahydroquinolines under mild reaction conditions. The methodology demonstrates broad substrate scope good functional group tolerance, representing notable advancement organic synthesis. Mechanistic experiments are performed clarify how occurs, indicating crucial role acid. DFT calculations supports observations, elucidating ring barrier overcome via coordination hydrogen bond interaction Imines often as directing/chelating groups C(sp3)–H activations due their installation removal, but have context given intermediate that would follow. Here, authors report catalysis, acid, which putatively reduces necessity intermediate.

Language: Английский

Citations

1
Synthesis of Chiral Saturated Heterocycles Bearing Quaternary Centers via Enantioselective β-C(sp3)–H Activation of Lactams DOI
Peng Lu,

William R. Burgenson,

Bryan J. Simmons

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 147(2), P. 1427 - 1433

Published: Dec. 31, 2024

The development of catalytic methods for the synthesis enantiopure saturated heterocycles has been a long-standing challenge in asymmetric catalysis. We describe first highly enantioselective palladium-catalyzed β-C(sp3)-H arylation and olefination lactams preparation various chiral N-heterocycles bearing quaternary carbon centers. presence strongly electron-withdrawing groups on bifunctional MPAThio ligand is crucial to reactivity weakly coordinating lactams. resulting enantioenriched are readily converted family piperidines imides that desirable drug discovery.

Language: Английский

Citations

1
Palladium Catalyzed ortho-C(sp2)–H Activation/Cyclization of Aryl Amines Assisted by Imine Directing Group and Vinylacetic Acid DOI Creative Commons
Huanfeng Jiang,

Xiangwen Tan,

Yaru Jing

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 20, 2024

Abstract Palladium-catalyzed directed C − H functionalization/cyclization is an effective approach for synthesizing nitrogen heterocycles. Imine, known its ease of installation/removal, has been extensively used in the C–H activation aldehydes, ketones and alkylamines. Nevertheless, it rarely explored C(sp2)–H aryl amines because generation a strained four-membered palladacycle. Herein, imine palladium catalyzed functionalization assisted by vinylacetic acid established, providing access to variety γ-lactone fused tetrahydroquinolines under mild reaction conditions. The methodology demonstrates broad substrate scope good functional group tolerance, representing notable advancement organic synthesis. Mechanistic experiments were performed clarify how occurred, indicating crucial role acid. DFT calculations supported observations, elucidating ring barrier was overcome via coordination hydrogen bond interaction

Language: Английский

Citations

0
Non‐Directed C−H Arylation of Anisole Derivatives via Pd/S,O‐Ligand Catalysis DOI Creative Commons

Kezuan Deng,

Verena Sukowski, M.A. Fernandez-Ibanez

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(19)

Published: Feb. 24, 2024

Abstract Non‐directed C−H arylation is one of the most efficient methods to synthesize biaryl compounds without need prefuctionalization starting materials, or installment and removal directing groups on substrate. A direct simple arenes as limiting reactants remains a challenge. Here we disclose non‐directed anisole derivatives reagents with aryl iodides under mild reaction conditions. The arylated products are obtained in synthetically useful yields bioactive molecules also demonstrated. Key success this methodology use one‐step synthesized S,O‐ligand.

Language: Английский

Citations

0