A catalytic alkene insertion approach to bicyclo[2.1.1]hexane bioisosteres

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(4), P. 535 - 541

Published: Feb. 13, 2023

Language: Английский

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Bicyclobutanes: from curiosities to versatile reagents and covalent warheads

Chemical Science, Journal Year: 2022, Volume and Issue: 13(40), P. 11721 - 11737

Published: Jan. 1, 2022

A flurry of reports for preparing, functionalizing, and using bicyclo[1.1.0]butanes (BCBs) have positioned them to be powerful synthons with numerous applications. This review discusses the recent developments regarding this strained carbocycle.

Language: Английский

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Synthesis of meta-substituted arene bioisosteres from [3.1.1]propellane

Nature, Journal Year: 2022, Volume and Issue: 611(7937), P. 721 - 726

Published: Sept. 15, 2022

Language: Английский

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Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis

Communications Chemistry, Journal Year: 2023, Volume and Issue: 6(1)

Published: Jan. 12, 2023

Abstract Bicyclobutanes are among the most highly strained isolable organic compounds and their associated low activation barriers to reactivity make them intriguing building-blocks in chemistry. In recent years, numerous creative synthetic strategies exploiting heightened have been presented these discoveries often gone hand-in-hand with development of more practical routes for synthesis. Their proclivity as strain-release reagents through weak central C–C bond has harnessed a variety addition, rearrangement insertion reactions, providing rapid access rich tapestry complex molecular scaffolds. This review will provide an overview different options available bicyclobutane synthesis, main classes that can be prepared from bicyclobutanes, modes used.

Language: Английский

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Photochemical Intermolecular [3σ + 2σ]-Cycloaddition for the Construction of Aminobicyclo[3.1.1]heptanes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(51), P. 23685 - 23690

Published: Dec. 16, 2022

The development of synthetic strategies for the preparation bioisosteric compounds is a demanding undertaking in medicinal chemistry. Numerous have been developed synthesis bicyclo[1.1.1]pentanes (BCPs), bridge-substituted BCPs, and bicyclo[2.1.1]hexanes. However, progress on bicyclo[3.1.1]heptanes, which serve as meta-substituted arene bioisosteres, has not previously explored. Herein, we disclose first photoinduced [3σ + 2σ] cycloaddition trisubstituted bicyclo[3.1.1]heptanes using bicyclo[1.1.0]butanes cyclopropylamines. This transformation only uses mild operationally simple conditions but also provides unique bioisosteres. applicability this method showcased by derivatization reactions.

Language: Английский

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Energy transfer photocatalysis: exciting modes of reactivity

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1068 - 1089

Published: Jan. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Language: Английский

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Strain-Release Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20716 - 20732

Published: Sept. 15, 2023

The concept of strain in organic compounds is as old modern chemistry and was initially introduced to justify the synthetic setbacks along synthesis small ring systems (pars construens strain). In last decades, chemists have developed an arsenal strain-release reactions destruens strain) which can generate─with significant driving force─rigid aliphatic that act three-dimensional alternatives (hetero)arenes. Photocatalysis added additional dimension processes by leveraging energy photons create chemical complexity under mild conditions. This perspective presents latest advancements photocatalysis─with emphases on mechanisms, catalytic cycles, current limitations─the unique architectures be produced, possible future directions.

Language: Английский

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Synthesis of Polysubstituted 2-Oxabicyclo[2.1.1]hexanes via Visible-Light-Induced Energy Transfer

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20207 - 20213

Published: Oct. 27, 2022

Synthesis of bicyclic scaffolds has attracted growing interest because they are high importance in modern pharmaceutical development. Here we report a strategy to access polysubstituted 2-oxabicyclo[2.1.1]hexanes single operation from readily accessible benzoylformate esters and bicyclo[1.1.0]butanes via visible-light-induced triplet energy transfer catalysis. The process is proposed involve formal [2π + 2σ] photocycloaddition/backbone C-H abstraction/aryl group migration sequence. A diverse range (hetero)aryl groups successfully underwent the backbone (C2) position provide previously inaccessible molecules, ester product can serve as handle for downstream manipulation, thus offering opportunities rapidly build up molecular complexity new sp3-rich chemical space.

Language: Английский

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Selective [2σ + 2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4304 - 4310

Published: Feb. 10, 2023

In contrast to the traditional and widely-used cycloaddition reactions involving at least a π bond component, [2σ + 2σ] radical between bicyclo[1.1.0]butanes (BCBs) cyclopropyl ketones has been developed provide modular, concise, atom-economical synthetic route substituted bicyclo[3.1.1]heptane (BCH) derivatives that are 3D bioisosteres of benzenes core skeleton number terpene natural products. The reaction was catalyzed by combination simple tetraalkoxydiboron(4) compound B2pin2 3-pentyl isonicotinate. broad substrate scope demonstrated synthesizing series new highly functionalized BCHs with up six substituents on 99% isolated yield. Computational mechanistic investigations supported pyridine-assisted boronyl catalytic cycle.

Language: Английский

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ortho-Selective Dearomative [2π + 2σ] Photocycloadditions of Bicyclic Aza-Arenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12324 - 12332

Published: May 26, 2023

Dearomative photocycloadditions are valuable chemical transformations, serving as an efficient platform to create three-dimensional molecular complexity. However, the photolability of original addition product especially within context ortho cycloadditions often causes undesired consecutive rearrangements, rendering these cycloadducts elusive. Herein, we report ortho-selective intermolecular photocycloaddition bicyclic aza-arenes including (iso)quinolines, quinazolines, and quinoxalines by utilizing a strain-release approach. With bicyclo[1.1.0]butanes coupling partners, this dearomative [2π + 2σ] cycloaddition enables straightforward construction C(sp3)-rich bicyclo[2.1.1]hexanes directly connected N-heteroarenes. Photophysical experiments DFT calculations revealed origin selectivity indicate that, in originally proposed energy transfer or direct excitation pathways, chain reaction mechanism is operative depending on conditions.

Language: Английский

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