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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Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters

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

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

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Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16859 - 16872

Published: June 27, 2020

The stereospecific 1,2-migration of boronate complexes is one the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals natural products. Typically, driven by displacement an α-leaving group, oxidation α-boryl radical, or electrophilic activation alkenyl complex. aim this article summarize recent advances rapidly expanding field electrophile-induced groups sp

Language: Английский

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Small rings in the bigger picture: ring expansion of three- and four-membered rings to access larger all-carbon cyclic systems

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7513 - 7538

Published: Jan. 1, 2021

Ring-expansion of strained small-size rings to forge larger all-carbon ones, allows a rapid build-up molecular complexity.

Language: Английский

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Photosensitized [2+2]‐Cycloadditions of Alkenylboronates and Alkenes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 21, 2022

A new strategy for the synthesis of highly versatile cyclobutylboronates via photosensitized [2+2]-cycloaddition alkenylboronates and alkenes is presented. The process mechanistically different from other processes in that energy transfer occurs with alkenylboronate as opposed to alkene. This allows an array diverse cyclobutylboronates. conversion these adducts compounds well their utility melicodenine C demonstrated.

Language: Английский

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Palladium-catalyzed selective alkoxycarbonylation of different alcohols toward the direct synthesis of cyclobutanecarboxylates

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115956 - 115956

Published: Jan. 1, 2025

Language: Английский

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α‐Selective Ring‐Opening Reactions of Bicyclo[1.1.0]butyl Boronic Ester with Nucleophiles

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(1), P. 212 - 216

Published: Sept. 21, 2020

Abstract The reaction of bicyclo[1.1.0]butyl pinacol boronic ester (BCB‐Bpin) with nucleophiles has been studied. Unlike BCBs bearing electron‐withdrawing groups, which react at the β‐position, BCB‐Bpin reacts a diverse set heteroatom (O, S, N)‐centred exclusively α‐position. Aliphatic alcohols, phenols, carboxylic acids, thiols and sulfonamides were found to be competent nucleophiles, providing ready access α‐heteroatom‐substituted cyclobutyl esters. In contrast, sterically hindered bis‐sulfonamides related reacted β′‐position leading cyclopropanes high trans‐selectivity. origin selectivity is discussed.

Language: Английский

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Construction of Complex Cyclobutane Building Blocks by Photosensitized [2 + 2] Cycloaddition of Vinyl Boronate Esters

Organic Letters, Journal Year: 2021, Volume and Issue: 23(9), P. 3496 - 3501

Published: April 12, 2021

Cyclobutyl moieties in drug molecules are rare, and general, they minimally substituted stereochemically simple. Methods to assemble structurally complex cyclobutane building blocks suitable for rapid diversification thus highly desirable. We report herein a photosensitized [2 + 2] cycloaddition with vinyl boronate esters affording straightforward access complex, densely functionalized scaffolds. Mechanistic studies suggest an activation mode involving energy transfer the styrenyl alkene rather than ester.

Language: Английский

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Boronic Ester Enabled [2 + 2]-Cycloadditions by Temporary Coordination: Synthesis of Artochamin J and Piperarborenine B

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(41), P. 18790 - 18796

Published: Oct. 6, 2022

A strategy for the photosensitized cycloaddition of alkenylboronates and allylic alcohols by a temporary coordination is presented. The process allows synthesis diverse range cyclobutylboronates. Key to development these reactions alcohol Bpin unit. This not only reaction proceed in an intramolecular manner but also high levels stereo regiocontrol. key aspect studies utility cycloadducts complex natural products artochamin J piperarborenine B.

Language: Английский

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Decarboxylation of β-boryl NHPI esters enables radical 1,2-boron shift for the assembly of versatile organoborons

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 14, 2023

In recent years, numerous 1,2-R shift (R = aliphatic or aryl) based on tetracoordinate boron species have been well investigated. the contrary, corresponding radical migrations, especially 1,2-boryl for construction of organoborons is still in its infancy. Given paucity and significance such strategies chemistry, it urgent to develop other efficient alternative synthetic protocols enrich these underdeveloped 1,2-boron before their fundamental potential applications could be fully explored at will. Herein, we demonstrated a visible-light-induced photoredox neutral decarboxylative cross-coupling reaction, which undergoes give translocated C-radical further capture versatile acceptors. The mild reaction conditions, good functional-group tolerance, broad β-boryl NHPI esters scope as acceptors make this protocol applicable modification bioactive molecules. It can expected that methodology will very useful tool an strategy primary via novel mode.

Language: Английский

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