Modular access to saturated bioisosteres of anilines via photoelectrochemical decarboxylative C(sp3)–N coupling

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 22, 2025

Language: Английский

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Late-Stage N-Atom Deletion of Multisubstituted 2-Azabicyclo[2.1.1]Hexanes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5825 - 5834

Published: March 25, 2025

Rigid three-dimensional scaffolds such as 2-azabicyclo[2.1.1]hexanes (aza-BCHs) and bicyclo[1.1.1]pentanes (BCPs) serve unique saturated isosteres of arenes, offering distinct substitution patterns due to their differing molecular exit vectors. This study introduces a skeletal editing strategy that efficiently transforms multisubstituted aza-BCHs into BCPs via an O-diphenylphosphinylhydroxylamine-promoted N-atom deletion process. method effectively addresses the challenge creating sterically hindered (2°)C–C(3°) bonds by removing nitrogen atom encased within bulky alkyl groups, reconstructing strained aza-BCH structure more BCP without generating undesired ring-opening diene byproducts. The used can be prepared from modified intermolecular [3 + 2] cycloaddition between bicyclo[1.1.0]butanes imines, making this practical. approach achieves remarkable efficiency, with yields up 99% scalability decagram quantities. resulting carboxylates further functionalized through decarboxylation, highlighting potential for programmed divergent synthesis BCPs. broad substrate scope high functional group tolerance protocol emphasize its versatility, it particularly valuable late-stage contained peptides, natural products, pharmaceuticals.

Language: Английский

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Rapid access to 3-substituted bicyclo[1.1.1]pentanes

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102537 - 102537

Published: April 1, 2025

Language: Английский

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Catalytic Selective Functionalization of Poly(organoborons)^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 28, 2024

Comprehensive Summary Organoborons are commonly used building blocks for rapidly increasing molecular complexity. Although significant progress has been made in the selective functionalization of mono‐organoborons, site‐selective poly(organoborons) attracted substantial interest organic synthesis, pharmaceuticals, and agrochemicals due to presence multiple potential reaction sites. This review discusses various activation modes target C–B bond, with diverse transformations being achieved both a efficient manner. Recent advances catalytic 1, n ‐diboronates through ionic radical pathways highlighted. Furthermore, we summarize existing challenges future research directions this field. Key Scientists In 1993, Suzuki, Miyaura coworkers developed pioneering example arylation towards cis‐1,2‐bis(boryl) alkenes, marking inception The Morken group contributions asymmetric diboration alkenes realized elegant these compounds since 2004. 2016, Fernández colleagues internal bond tri(boronates). Since 2019, Aggarwal Giese‐type addition at more substituted 1,2‐bis(boronic) esters photoredox catalysis. controllable regiodivergent alkynylation 1,3‐bis(boronic) was by Gao 2023. Recently, Qin conducted on programmable late‐stage bridge‐substituted bicyclo[1.1.1]pentane (BCP) bis‐boronates. 2013, stereoselective have several groups, including those led Chen. summarizes latest most developments field 1993.

Language: Английский

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Asymmetric synthesis of atropisomers featuring cyclobutane boronic esters facilitated by ring-strained B-ate complexes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Dec. 30, 2024

The strain-release-driven reactions of bicyclo[1.1.0]butanes (BCBs) have received significant attention from chemists. Notably, 1,2-migratory enabled by BCB-derived B-ate complexes effectively complement the initiated common BCBs. desired products are particularly valuable for late-stage transformations due to presence C-B bond. However, asymmetric mediated boronate progressed slowly. In this study, we develop an synthesis atropisomers featuring cis-cyclobutane boronic esters facilitated 1,2-carbon or boron migration ring-strained complexes, achieving high enantioselectivity. reaction is compatible with various aryl, alkenyl, alkyl and B

Language: Английский

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Borylated cyclobutanes via thermal [2 + 2]-cycloaddition

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3249 - 3254

Published: Jan. 1, 2024

A one-step approach to borylated cyclobutanes from amides of carboxylic acids and vinyl boronates is elaborated. The reaction proceeds via the thermal [2 + 2]-cycloaddition in situ -generated keteniminium salts.

Language: Английский

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Organometallic Bridge Diversification of Bicyclo[1.1.1]pentanes

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(12)

Published: Dec. 20, 2023

Abstract Bicyclo[1.1.1]pentane (BCP) derivatives have attracted significant recent interest in drug discovery as alkyne, tert ‐butyl and arene bioisosteres, where their incorporation is frequently associated with increased compound solubility metabolic stability. While strategies for functionalisation of the bridgehead (1,3) positions are extensively developed, platforms allowing divergent substitution at bridge (2,4,5) remain limited. Recent reports introduced 1‐electron arylation a small range other substituents, but limited terms scope, yields or practical complexity. Herein, we show synthesis diverse 1,2,3‐trifunctionalised BCPs through lithium‐halogen exchange readily accessible BCP bromide. When coupled medicinally relevant product derivatisations, our developed 2‐electron “late stage” approach provides rapid straightforward access to unprecedented structural diversity (>20 hitherto‐unknown motifs reported). Additionally, describe method enantioenriched “chiral‐at‐BCP” bicyclo[1.1.1]pentanes novel stereoselective desymmetrisation.

Language: Английский

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Regioselective Alkynylation and Alkenylation at the More Hindered C–B Bond of 1,2-Bis(Boronic) Esters

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1595 - 1600

Published: Feb. 19, 2024

Selective transformations at the more sterically hindered sites of organic molecules represent a frontier in ability to precisely modify molecules. The lack effective synthetic methods stands stark contrast large number encumbered encountered interest. Here, we demonstrate that 1,2-bis(boronates) undergo selective alkynylation and alkenylation C-B bond. Our preliminary mechanistic studies disclosed this reaction can proceed through two convergent pathways involving direct coupling site versus 1,2-boron migratory coupling. Notably, method facilitated convenient access alkenyl alkynyl boron products, which be diversified by an array transformations.

Language: Английский

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Photoinduced Decarboxylative Borylation of N-Hydroxyphthalimide Esters with Hypoboric Acid

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2292 - 2296

Published: March 13, 2024

We developed a visible-light-driven photochemical transformation in which activated primary, secondary, and tertiary alkylcarboxylic acids were converted into the corresponding boronic esters absence of catechol any added photocatalyst. The procedure relies on utilization hypoboric acid redox-active to ensure simple economic procedure. Quantum chemical calculations mechanistic considerations provide deeper insights mechanism borylation reactions.

Language: Английский

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Platinum‐Catalyzed Regio‐ and Enantioselective Diboration of Unactivated Alkenes with (pin)B−B(dan)

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Aug. 14, 2024

Asymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization the less hindered primary boronic ester commonly achieved. Conversely, sterically accessible secondary remains challenging. An alternative way to control chemoselective bis(boron) compounds by engendering different Lewis acidity two boryl moieties, since reactivity would then be dictated instead sterics. We report herein regio- enantioselective Pt-catalyzed unactivated with (pin)B-B(dan). A broad range cyclic undergo furnish differentiable 1,2-bis(boron) high levels enantiocontrol, giving access a wide variety novel building blocks from common intermediate. The reaction places acidic B(dan) group at position resulting 1,2-bisboryl alkanes transformations B(pin) located more position. regioselectivity has been studied DFT calculations believed originate trans influence, which lowers activation barrier for formation regioisomer that weaker electron donor [B(pin) vs B(dan)] opposite strong (alkyl group) in platinum complex.

Language: Английский

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