The Rise of Boron-Containing Compounds: Advancements in Synthesis, Medicinal Chemistry, and Emerging Pharmacology

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(5), P. 2441 - 2511

Published: Feb. 21, 2024

Boron-containing compounds (BCC) have emerged as important pharmacophores. To date, five BCC drugs (including boronic acids and boroles) been approved by the FDA for treatment of cancer, infections, atopic dermatitis, while some natural are included in dietary supplements. Boron's Lewis acidity facilitates a mechanism action via formation reversible covalent bonds within active site target proteins. Boron has also employed development fluorophores, such BODIPY imaging, carboranes that potential neutron capture therapy agents well novel diagnostics therapy. The utility synthetic become multifaceted, breadth their applications continues to expand. This review covers many uses targets boron medicinal chemistry.

Language: Английский

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Electrocatalytic hydrogen evolution with a copper porphyrin bearing meso-(o-carborane) substituents

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(72), P. 10777 - 10780

Published: Jan. 1, 2023

A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis(o-carborane)porphyrin (1) was synthesized and tested for the electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) HER by shifting catalytic wave to anodic direction 190 mV. aqueous media, also outperformed 2 achieving higher current densities under smaller overpotentials. This enhancement attributed aromatic strong electron-withdrawing properties o-carborane groups. work is significant address crucial effects meso-(o-carborane) substituents metal porphyrins on boosting HER.

Language: Английский

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Supramolecular Architectures Bearing Half-Sandwich Iridium- or Rhodium-Based Carboranes: Design, Synthesis, and Applications

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19440 - 19457

Published: Aug. 29, 2023

The utilization of carboranes in supramolecular chemistry has attracted considerable attention. unique spatial configuration and weak interaction forces can help to explore the properties complexes, particularly via host–guest chemistry. Additionally, certain difficulties encountered carborane development─such as controlled B–H bond activation─can be overcome by judiciously selecting metal centers their adjacent ligands. However, few studies are being conducted this nascent research area. With advances field, novel carborane-based complexes will likely prepared, structurally characterized, intrinsically investigated. To expedite these efforts, we present major findings from recent studies, including π–π interactions, associations, steric effects, which have been leveraged implement a regioselective process for activating B(2,9)–, B(2,8)–, B(2,7)–H bonds para-carboranes B(4,7)–H ortho-carboranes. Future should clarify interactions potential enhancing utility complexes. Although exhibit several (such dihydrogen-bond [Bδ+–Hδ−···Hδ+–Cδ−], Bδ+–Hδ−···M+, Bδ+–Hδ−···π interactions), manner they utilized remains unclear. Supramolecular those based on chemistry, platform demonstrating applications interactions. Owing importance alkane separation, related recognition separation isomers primarily summarized. Advances certainly lead more possibilities

Language: Английский

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Organocatalytic Asymmetric Synthesis of o-Carboranyl Amines

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

Published: Jan. 14, 2025

Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.

Language: Английский

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Synthesis and Stability of o-Carborane-Fused Phospholes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Herein, we report that ArLi, formed in situ through the Li/Br exchange between aryl bromide and n-butyllithium, can undergo rapid intramolecular Li/H(Ccage–H) to functionalize o-carboranes. Based on this observation, a dual C–H lithiation reaction of 2- or 3-o-carboryl benzothiophenes was developed, series o-carborane-fused phospholes were synthesized by dilithio compounds with chlorophosphine. This is simple high chemical selectivity medium yields. It also be applied furan derivative. Stability studies demonstrated these phosphole derivatives are stable both trivalent coordination states for phosphorus. In contrast, their oxides sensitive moisture air susceptible attack nucleophiles, leading breakage Ccage-P bond. Computational results indicate newly generated rings have weak aromaticity.

Language: Английский

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Skeletal Transformation of Unactivated Arenes Enabled by a Low-Temperature Dearomative (3 + 2) Cycloaddition

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12214 - 12223

Published: May 24, 2023

Simple aromatic compounds like benzene are abundant feedstocks, for which the preparation of derivatives chiefly begins with electrophilic substitution reactions or, less frequently, reductions. Their high stability makes them particularly reluctant to participate in cycloadditions under ordinary reaction conditions. Here, we demonstrate exceptional ability 1,3-diaza-2-azoniaallene cations undergo formal (3 + 2) unactivated below room temperature, providing thermally stable dearomatized adducts on a multi-gram scale. The cycloaddition, tolerates polar functional groups, activates ring toward further elaboration. On treatment dienophiles, cycloadducts (4 cycloaddition–cycloreversion cascade yield substituted or fused arenes, including naphthalene derivatives. overall sequence results transmutation arenes through an exchange carbons: two-carbon fragment from original is replaced another incoming dienophile, introducing unconventional disconnection synthesis ubiquitous building blocks. Applications this two-step acenes, isotopically labeled molecules, and medicinally relevant demonstrated.

Language: Английский

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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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Towards the Application of Purely Inorganic Icosahedral Boron Clusters in Emerging Nanomedicine

Molecules, Journal Year: 2023, Volume and Issue: 28(11), P. 4449 - 4449

Published: May 30, 2023

Traditionally, drugs were obtained by extraction from medicinal plants, but more recently also organic synthesis. Today, chemistry continues to focus on compounds and the majority of commercially available are molecules, which can incorporate nitrogen, oxygen, halogens, as well carbon hydrogen. Aromatic that play important roles in biochemistry find numerous applications ranging drug delivery nanotechnology or biomarkers. We achieved a major accomplishment demonstrating experimentally/theoretically boranes, carboranes, metallabis(dicarbollides), exhibit global 3D aromaticity. Based stability–aromaticity relationship, progress made synthesis derivatized clusters, we have opened up new boron icosahedral clusters key components field novel healthcare materials. In this brief review, present results at Laboratory Inorganic Materials Catalysis (LMI) Institut de Ciència Barcelona (ICMAB-CSIC) with clusters. These geometric shape semi-metallic nature presence exo-cluster hydrogen atoms interact biomolecules through non-covalent dihydrogen bonds, role endowing these unique properties largely unexplored (bio)materials.

Language: Английский

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Visible‐Light‐Induced Photoreduction of Carborane Phosphonium Salts: Efficient Synthesis of Carborane‐Oxindole‐Pharmaceutical Hybrids

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: April 29, 2023

Visible-light-induced photoreaction of carboranes is an effective approach to prepare carborane-containing compounds. While several methods involving boron-centered carboranyl radicals have been established, those for carbon-centered are underdeveloped, except the UV-light-promoted photohomolysis. Herein, we describe a simple but access by photoreduction carborane phosphonium salts under blue light irradiation without using transition metals and photocatalysts. The utility method was demonstrated successfully preparing range carborane-oxindole-pharmaceutical hybrids radical cascade reactions. Computational experimental studies suggest that generated single-electron transfer photoactive charge-transfer complexes between additive potassium acetate.

Language: Английский

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Highly selective electrophilic B(9)-amination of o-carborane driven by HOTf and HFIP

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 4975 - 4980

Published: Jan. 1, 2022

An efficient B(9) electrophilic amination of o -carboranes with azodicarboxylates, promoted by a Brønsted acid and HFIP, was developed.

Language: Английский

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