A variable bidentate traceless directing group for nickel-catalyzed regioselective B–H poly-chalcogenation of o-carboranes

Inorganic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A nickel-catalyzed direct cage B–H poly-chalcogenation of icosahedral carborane clusters, enabled by a variable bidentate 8-aminoquinoline traceless directing group, has been developed under oxidant-free and weakly basic conditions.

Language: Английский

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Directing Group Assisted Transition Metal Catalyzed Selective BH Functionalization of o-Carboranes

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

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Palladium-Catalyzed Regioselective B(3,4,5,6)–H Tetra-Arylation of o-Carboranes

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 21, 2025

A transition-metal-catalyzed iterative multiple cage B-H activation reaction for constructing multifunctionalization of o-carboranes in one pot is challenging. Herein, palladium-catalyzed regioselective tetra-arylation a wide range C(1)-N-aryl-o-carboranyl amides with aryl iodides has been developed. variety B(3,4,5,6)-tetra-arylated were synthesized good-to-excellent yields. Moreover, the mono-, di-, and triarylated intermediate products isolated, exact structures determined by NMR, high-resolution mass spectrometry, X-ray analysis, which provide rationale that order introduction groups into o-carborane B(4) > B(5) B(3)/B(6). This protocol represents powerful synthetic method polyfunctionalization derivatives under very mild simple conditions, offers valuable reference design synthesis molecular propellers based on carboranes.

Language: Английский

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A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

The palladium-catalyzed generation of bis(o-carborane)s via regioselective B-B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential B4-H activation, B4'-H/B5'-H and reductive elimination, yielding ultimately. palladium catalyst tends to experience a Pd(II) → Pd(0) rather than Pd(IV) catalytic cycle, in which second B-H (B4'-H/B5'-H) activation serves as rate-determining step (RDS). Computed RDS step's barriers (27.0/29.0 kcal·mol-1, TS2a_I/TS2a'_I) consist well with experimental yields selectivities (P1a:P2a = 57%:23%). regioselectivity primarily controlled process, electronic effect playing key role steric hindrance influencing somewhat, confirmed natural bond orbital (NBO) noncovalent interaction (NCI) analyses. free-energy (27.0/29.6/31.1 kcal·mol-1) for AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted a_II), AgOAc-assisted a_III) cases agree perfectly corresponding trends (obtained 57%/43%/12% P1a, respectively). Theoretical predictions substituent effects also demonstrate consistency observations. This perfect agreement between experiments computations validates providing crucial insights into o-carboranes thus aiding controllable synthesis carborane materials.

Language: Английский

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9,9′-Bis-o-carboranes: synthesis and exploration of properties

Chemical Communications, Journal Year: 2023, Volume and Issue: 60(5), P. 614 - 617

Published: Dec. 6, 2023

A highly efficient Pd-catalyzed B(9)-H/B(9)-H oxidative dehydrogenation coupling of carboranes to synthesize 9,9'-bis-

Language: Английский

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