Synthesis of polysubstituted bicyclo[2.1.1]hexanes enabling access to new chemical space DOI Creative Commons

Marius Reinhold,

Justin Steinebach,

Christopher Golz

и другие.

Chemical Science, Год журнала: 2023, Номер 14(36), С. 9885 - 9891

Опубликована: Янв. 1, 2023

Crossed [2 + 2] cycloaddition yields bicyclo[2.1.1]hexanes with 11 different substitution patterns. ortho -, meta - and polysubstituted benzene bioisosteres, structures substituent patterns that go beyond aromatic chemical space can be prepared.

Язык: Английский

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

Soumitra Agasti,

Frédéric Beltran,

Emma Pye

и другие.

Nature Chemistry, Год журнала: 2023, Номер 15(4), С. 535 - 541

Опубликована: Фев. 13, 2023

Язык: Английский

Процитировано

166

Bicyclobutanes: from curiosities to versatile reagents and covalent warheads DOI Creative Commons
Christopher B. Kelly, John A. Milligan, Leon J. Tilley

и другие.

Chemical Science, Год журнала: 2022, Номер 13(40), С. 11721 - 11737

Опубликована: Янв. 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.

Язык: Английский

Процитировано

153

Synthesis of meta-substituted arene bioisosteres from [3.1.1]propellane DOI
Nils Frank, Jeremy Nugent,

Bethany R. Shire

и другие.

Nature, Год журнала: 2022, Номер 611(7937), С. 721 - 726

Опубликована: Сен. 15, 2022

Язык: Английский

Процитировано

143

Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis DOI Creative Commons
Maxim Golfmann, Johannes C. L. Walker

Communications Chemistry, Год журнала: 2023, Номер 6(1)

Опубликована: Янв. 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.

Язык: Английский

Процитировано

137

Photochemical Intermolecular [3σ + 2σ]-Cycloaddition for the Construction of Aminobicyclo[3.1.1]heptanes DOI
Yongxiang Zheng, Weichen Huang,

Roshan K. Dhungana

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(51), С. 23685 - 23690

Опубликована: Дек. 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.

Язык: Английский

Процитировано

135

Energy transfer photocatalysis: exciting modes of reactivity DOI
Subhabrata Dutta, Johannes E. Erchinger, Felix Strieth‐Kalthoff

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(3), С. 1068 - 1089

Опубликована: Янв. 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.

Язык: Английский

Процитировано

135

Strain-Release Photocatalysis DOI
Peter Bellotti, Frank Glorius

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(38), С. 20716 - 20732

Опубликована: Сен. 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.

Язык: Английский

Процитировано

130

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

Roman Kleinmans,

Constantin G. Daniliuc

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(44), С. 20207 - 20213

Опубликована: Окт. 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.

Язык: Английский

Процитировано

123

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

Tao Yu,

Jinbo Yang, Zhijun Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 4304 - 4310

Опубликована: Фев. 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.

Язык: Английский

Процитировано

122

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

Roman Kleinmans,

Subhabrata Dutta,

Kristers Ozols

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(22), С. 12324 - 12332

Опубликована: Май 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.

Язык: Английский

Процитировано

120