Iridium(III)-catalyzed remote B(9)−H alkylation of o-carboranes with nitrile template DOI Creative Commons
Phil Ho Lee, Kyungsup Lee, Ji‐Won Kim

et al.

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

Published: July 24, 2024

Abstract Although the directing group assisted ortho-B − H activation reactions of o-carboranes have been well established during past decade, meta-B are unexplored so far. Herein, iridium(III)-catalyzed remote B(9) alkylation with nitrile template demonstrated for first time. It was revealed that fine tuning structures is essential high reaction efficiency and regioselectivity. This process exhibits a broad substrate scope good functional tolerance under simple conditions. The template, readily accessible from o-carborane acids, can be removed conveniently after completion reaction. present method provides powerful synthetic route to complex derivatives, demonstrating successful larger scale further molecular transformations B(9)-alkylated products.

Language: Английский

Directing Group Assisted Transition Metal Catalyzed Selective BH Functionalization of o-Carboranes DOI
Zuowei Xie, Jie Zhang

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

Published: June 11, 2024

Abstract Carboranes are a type of molecular clusters consisting carbon, hydrogen, and boron atoms. They possess unique characteristics, such as three-dimensional aromaticity, icosahedral geometry, robustness. Functionalized carboranes have been utilized in various fields, including medicine, materials, organometallic/coordination chemistry. In this context, selective functionalization o-carboranes has received tremendous attention, specifically the regio- enantioselective modification ten chemically similar BH vertices within carborane cage. recent years, significant progress made catalytic vertex-specific functionalization, well achieving cage BH. This review provides an overview advancements research field. 1 Introduction 2 Carboxy-Assisted Functionalization 2.1 Formation B–C Bonds 2.2 B–N 2.3 B–O 2.4 B–X 2.5 Consecutive B–Y (Y = N, O) 3 N-Based Directing-Group-Assisted B–H 3.1 Acylamino Directing Group 3.2 Amide 3.3 Pyridyl 3.4 Imine 4 Phosphinyl-Assisted Cage 5 Bidentate-Directing-Group-Assisted 6 Other 7 Conclusions

Language: Английский

Citations

3
Iridium-Catalyzed Regioselective B(4)-Alkenylation and B(3,5)-Dialkenylation of o-Carboranes DOI
Hee Chan Noh, Cheol‐Eui Kim, Kyungsup Lee

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6643 - 6648

Published: Aug. 30, 2023

Iridium(I)-catalyzed regioselective B(4)-alkenylation has been developed from o-carboranyl sulfoxonium ylides and alkynes through B(4)–H activation. The sequential B(4)- B(6)-alkenylation afforded B(3,5)-dialkenylated in one pot. Eventually, two alkenyl groups, the same or different, were introduced at positions 3 5 of carborane. Sulfoxonium ylide used as a directing group remains available for further functionalization is converted to B-alkenylated trichloromethyl ketones.

Language: Английский

Citations

7
Iridium(III)-Catalyzed Regioselective B(4)–H Amination of o-Carboranes with Sufilimines DOI

Kyeongna Park,

Gi Uk Han, S.‐K. YOON

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(32), P. 5989 - 5994

Published: Aug. 4, 2023

Iridium(III)-catalyzed regioselective B(4)-H amination is developed from the reaction of o-carborane acids with sulfilimines without any oxidants under mild conditions, which leads to a wide range aminated o-carboranes in good yields broad substrate scope. Moreover, selective B(3,6)-diamination acid was achieved. The present attractive practical point view because dibenzothiophene quantitatively recovered and reused.

Language: Английский

Citations

5
Rhodium(III)-Catalyzed B(4)-Azo Coupling of o-Carboranes with Aryl Diazonium Tetrafluoroborates DOI
Kyungsup Lee, S.‐K. YOON, Hee Chan Noh

et al.

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

Published: Sept. 25, 2024

Rh(III)-catalyzed B(4)-azo coupling reactions of

Language: Английский

Citations

0
Ir‐Catalyzed B(3)‐Amination of o‐Carboranes with Amines via Acceptorless Dehydrogenative BH/NH Cross‐Coupling DOI Creative Commons
Yik Ki Au, Qiang‐Qiang Ma, Jie Zhang

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(20)

Published: Sept. 11, 2023

An efficient and convenient strategy for Ir-catalyzed selective B(3)-amination of o-carboranes with amines via acceptorless BH/NH dehydrocoupling was developed, affording a series B(3)-aminated-o-carboranes in moderate to high isolated yields H2 gas as sole by-product. Such an oxidant-free system endues the protocol sustainability, atom-economy environmental friendliness. A reaction mechanism Ir(I)-Ir(III)-Ir(I) catalytic cycle involving oxidative addition, dehydrogenation reductive elimination proposed.

Language: Английский

Citations

1
Experiment and Computational Study on Pd‐Catalyzed MIA‐Directed Ortho‐C‐H Alkynlation of Phenylalanine DOI
Fujie Zhang,

Yu Liang,

Donghui Liu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(7)

Published: May 9, 2024

Abstract The direct ortho ‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range substrates, resulting in efficient synthesis alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that fluoride ion enhances electropositivity Pd(IV) and interaction between C1 C2 within transition state reductive elimination, which significantly expedites elimination step process.

Language: Английский

Citations

0
Iridium(III)-catalyzed remote B(9)−H alkylation of o-carboranes with nitrile template DOI Creative Commons
Phil Ho Lee, Kyungsup Lee, Ji‐Won Kim

et al.

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

Published: July 24, 2024

Abstract Although the directing group assisted ortho-B − H activation reactions of o-carboranes have been well established during past decade, meta-B are unexplored so far. Herein, iridium(III)-catalyzed remote B(9) alkylation with nitrile template demonstrated for first time. It was revealed that fine tuning structures is essential high reaction efficiency and regioselectivity. This process exhibits a broad substrate scope good functional tolerance under simple conditions. The template, readily accessible from o-carborane acids, can be removed conveniently after completion reaction. present method provides powerful synthetic route to complex derivatives, demonstrating successful larger scale further molecular transformations B(9)-alkylated products.

Language: Английский

Citations

0