Synthesis of 1,4‐Naphthoquinones via Palladium(II)‐Catalyzed Tertiary C−H Alkylation of Olefins Followed by C−C Bond Cleavage DOI
Xu Zhang,

Mengfan Chang,

Tongtong Ni

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract An efficient method has been developed for the preparation of 1,4‐naphthoquinones via a palladium‐catalyzed reaction 2‐aryl‐1,3‐indandiones with olefins. This involves tertiary C−H alkylation olefins to produce alcohol, followed by C−C bond cleavage.

Language: Английский

Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination DOI
Xin Liu,

Qi Zhu,

Guangbin Dong

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 5, 2024

Since the discovery of palladium/norbornene (Pd/NBE)-catalyzed ortho amination in 2013, escaping limitation only yielding tertiary anilines has been a long-standing challenge. Here, we describe that, by carefully choosing phosphine ligand and NBE mediator, installation N-mono-alkylamino group becomes feasible. The reaction tolerates wide range aryl iodide substrates various N-mono-tertiary alkylamine-derived electrophiles. Both ipso alkenylation alkynylation can be realized. synthetic utility this method is exemplified formation primary amino via selective deprotection streamlined access to N-heterocycles. Preliminary success installing bulky N-secondary alkylamino mechanistic understanding decomposition pathways mono N-alkylamine electrophiles have obtained.

Language: Английский

Citations

8
Site-Selective C–H Arylation of 2-Pyridones via Pd/NBE Cooperative Catalysis DOI

Ziyi Sun,

Zibin Jiang,

Fengya He

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7762 - 7770

Published: May 3, 2024

The 4-aryl-2-pyridone scaffold is considered to be a privileged pharmacophore. Diversity-oriented synthesis of its derivatives pressing demand within the field medicinal chemistry. Herein, we report site-selective C–H arylation 2-pyridones via palladium/norbornene cooperative catalysis. success this research based on nucleophilicity and metalation properties exhibited by C5 position in 2-pyridones, an activated norbornene that was employed capture C5-palladation intermediate transfer it C4 position, resulting highly specific at position. This methodology showcases remarkable compatibility with readily available aryl bromides, enabling efficient diverse range functional scaffolds (46 examples) notable site selectivity, which will very useful drug discovery. Furthermore, approach successfully utilized for economically viable perlolidine analogues. Density theory calculations revealed preference bond activation 2-pyridones. In addition, insights into mechanism suggest oxidative addition reductive elimination bromides are crucial steps conversion.

Language: Английский

Citations

6
Silver-mediated intramolecular oxy- and aminodifluoroalkylation of unactivated alkenes with ethyl difluoroiodoacetate toward the synthesis of difluoroalkylated heterocycles DOI
Zhigang Huang, Cui Yang, Ziyang Duan

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: 172, P. 134465 - 134465

Published: Jan. 8, 2025

Language: Английский

Citations

0
Asymmetric Two‐Component Alkenyl Catellani Reaction for the Construction of C—N Axial Chirality† DOI
Chenggui Wu, Ze‐Shui Liu, Yongjia Shang

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(7), P. 699 - 704

Published: Nov. 29, 2023

Comprehensive Summary Herein, we report an asymmetric two‐component alkenyl Catellani reaction for the construction of C—N axial chirality through a palladium/chiral norbornene cooperative catalysis and axial‐to‐axial transfer process. Various partially aromatic iodinated 2‐pyridones, quinolones, coumarin uracil substrates react with 2,6‐disubstituted aryl bromides tethered amide group, to afford wide variety polycyclic atropisomers (38 examples, up 97% e.e. ). The obtained originates from preformed transient C—C high fidelity. synthetic utility this chemistry is demonstrated by facile preparation complex quinoline pyridine based N‐deprotection aromatization sequence. In addition, remote axial‐to‐central diastereoinduction process dictated observed excellent diastereocontrol.

Language: Английский

Citations

7
Stereodivergency in Copper‐Catalyzed Borylative Difunctionalizations: The Impact of Boron Coordination DOI Creative Commons
Bijan Mirabi, Shangyu Li, Justin Ching

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: Aug. 13, 2024

Abstract A reagent‐controlled diastereodivergent copper‐catalyzed borylative difunctionalization is reported. The formation of Lewis adducts that guide selectivity commonly invoked in organic reaction mechanisms. Using density functional theory calculations, we identified BpinBdan as a sterically similar and less acidic alternative to B 2 pin . newly developed aldol domino the proof‐of‐concept, demonstrate change stereochemical outcome by simple borylating reagent—B affords diastereomer associated with coordination control while overturns this mode binding. We show strategy can be generalized other scaffolds and, more importantly, does not alter diastereomeric when involved. viewed mechanistic probe for future borylation reactions.

Language: Английский

Citations

1
Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination DOI
Xin Liu,

Qi Zhu,

Guangbin Dong

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(24)

Published: April 5, 2024

Abstract Since the discovery of palladium/norbornene (Pd/NBE)‐catalyzed ortho amination in 2013, escaping limitation only yielding tertiary anilines has been a long‐standing challenge. Here, we describe that, by carefully choosing phosphine ligand and NBE mediator, installation N ‐mono‐alkylamino group becomes feasible. The reaction tolerates wide range aryl iodide substrates various ‐mono‐tertiary alkylamine‐derived electrophiles. Both ipso alkenylation alkynylation can be realized. synthetic utility this method is exemplified formation primary amino via selective deprotection streamlined access to ‐heterocycles. Preliminary success installing bulky ‐secondary alkylamino mechanistic understanding decomposition pathways mono ‐alkylamine electrophiles have obtained.

Language: Английский

Citations

0
Copper‐Catalyzed Cross‐Coupling of Acylzirconocenes and Diaryliodonium Salts: An Efficient Synthesis of Alkyl‐aryl‐ketones from Alkenes DOI

Simone Grosso,

Marcelina Mlynczak,

Gwilherm Evano

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(47)

Published: Oct. 30, 2023

Abstract An efficient and unprecedented cross‐coupling between acylzirconocenes, readily available starting materials conveniently prepared by hydrozirconation of alkenes a subsequent carbonylation with carbon monoxide, diaryliodonium tetrafluoroborates is reported. This procedure enables the synthesis broad variety alkyl‐aryl‐ketones upon simple catalysis copper cyanide without need additional ligands only requires low pressure monoxide generated in situ , two‐chamber reactor, from N ‐formylsaccharin.

Language: Английский

Citations

1
Stereodivergency in Copper‐Catalyzed Borylative Difunctionalizations: The Impact of Boron Coordination DOI Creative Commons
Bijan Mirabi, Shangyu Li, Justin Ching

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: Aug. 13, 2024

Abstract A reagent‐controlled diastereodivergent copper‐catalyzed borylative difunctionalization is reported. The formation of Lewis adducts that guide selectivity commonly invoked in organic reaction mechanisms. Using density functional theory calculations, we identified BpinBdan as a sterically similar and less acidic alternative to B 2 pin . newly developed aldol domino the proof‐of‐concept, demonstrate change stereochemical outcome by simple borylating reagent—B affords diastereomer associated with coordination control while overturns this mode binding. We show strategy can be generalized other scaffolds and, more importantly, does not alter diastereomeric when involved. viewed mechanistic probe for future borylation reactions.

Language: Английский

Citations

0
Direct Observation of β-Alkynyl Eliminations from Unstrained Propargylic Alkoxide Cu(I) Complexes by C-C Bond Cleavage DOI Creative Commons
Ba L. Tran, Jack T. Fuller, Jeremy D. Erickson

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

We report a comprehensive study on the synthesis, reactivity, mechanism, and computation for β-alkynyl eliminations of secondary tertiary propargylic alkoxides Cu( i ) complexes supported by N-heterocyclic carbenes diphosphines.

Language: Английский

Citations

0
Synthesis of 1,4‐Naphthoquinones via Palladium(II)‐Catalyzed Tertiary C−H Alkylation of Olefins Followed by C−C Bond Cleavage DOI
Xu Zhang,

Mengfan Chang,

Tongtong Ni

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract An efficient method has been developed for the preparation of 1,4‐naphthoquinones via a palladium‐catalyzed reaction 2‐aryl‐1,3‐indandiones with olefins. This involves tertiary C−H alkylation olefins to produce alcohol, followed by C−C bond cleavage.

Language: Английский

Citations

0