Difunctionalization of C–C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins DOI
Steven H. Bennett, Alexander Fawcett, Elliott H. Denton

и другие.

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(39), С. 16766 - 16775

Опубликована: Сен. 4, 2020

Difunctionalization reactions of C–C σ-bonds have the potential to streamline access molecules that would otherwise be difficult prepare. However, development such is challenging because are typically unreactive. Exploiting high ring-strain energy polycyclic carbocycles a common strategy weaken and facilitate reaction σ-bonds, but there limited examples highly strained being used in difunctionalization reactions. We demonstrate bicyclo[1.1.0]butyl boronate complexes (strain ca. 65 kcal/mol), which were prepared by reacting boronic esters with lithium, react electrophiles achieve diastereoselective central σ-bond unit. The shows broad substrate scope, range different successfully employed form diverse set 1,1,3-trisubstituted cyclobutanes (>50 examples) diastereoselectivity. diastereoselectivity observed has been rationalized based on combination experimental data DFT calculations, suggests separate concerted stepwise mechanisms operating, depending upon migrating substituent electrophile used.

Язык: Английский

Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer DOI

Roman Kleinmans,

Tobias Pinkert,

Subhabrata Dutta

и другие.

Nature, Год журнала: 2022, Номер 605(7910), С. 477 - 482

Опубликована: Март 21, 2022

Язык: Английский

Процитировано

262
Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts DOI

Sheila Namirembe,

James P. Morken

Chemical Society Reviews, Год журнала: 2019, Номер 48(13), С. 3464 - 3474

Опубликована: Янв. 1, 2019

This tutorial review describes recent developments in catalytic reaction design that involve catalyst-promoted 1,2-metalate shifts as a critical part of the mechanism.

Язык: Английский

Процитировано

215
Gold-Catalyzed Synthesis of Small Rings DOI Creative Commons
Mauro Mato, Allegra Franchino, Cristina García‐Morales

и другие.

Chemical Reviews, Год журнала: 2020, Номер 121(14), С. 8613 - 8684

Опубликована: Ноя. 2, 2020

Three- and four-membered rings, widespread motifs in nature medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool construct these highly strained carbocycles. This review aims provide comprehensive summary of all the major advances discoveries made gold-catalyzed synthesis cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, corresponding heterocyclic or heterosubstituted analogs.

Язык: Английский

Процитировано

187
Strain release – an old tool for new transformations DOI
Joanna Turkowska, Jakub Durka, Dorota Gryko

и другие.

Chemical Communications, Год журнала: 2020, Номер 56(43), С. 5718 - 5734

Опубликована: Янв. 1, 2020

This Feature Article provides an overview of research advances in the chemistry spring-loaded molecules, focusing mainly on strain-release transformations.

Язык: Английский

Процитировано

162
Radical Addition to Strained σ-Bonds Enables the Stereocontrolled Synthesis of Cyclobutyl Boronic Esters DOI
Mattia Silvi, Varinder K. Aggarwal

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(24), С. 9511 - 9515

Опубликована: Май 29, 2019

While radical additions to π-bonds are well established, σ-bonds far less explored. We have found that electron deficient radicals derived from alkyl iodides under visible light irradiation add the central strained bond of bicyclobutyl (BCB)-boronate complexes and lead 1,3-alkyl disubstituted cyclobutyl boronic esters in high yields, with full stereospecificity levels stereoselectivity. Novel cyclobutyl-substituted structures, including peptide steroid ester derivatives can be accessed. Additionally, although use electron-rich as precursors was ineffective, an alternative route involving alkylsulfonylation BCB-boronate followed by reductive desulfonylation provided access simple substituted cyclobutane products.

Язык: Английский

Процитировано

158
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

157
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

147
Beyond Bioisosteres: Divergent Synthesis of Azabicyclohexanes and Cyclobutenyl Amines from Bicyclobutanes** DOI

Kushal Dhake,

Kyla Woelk,

Joseph Becica

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(27)

Опубликована: Апрель 20, 2022

The development of two divergent and complementary Lewis acid catalyzed additions bicyclobutanes to imines is described. Microscale high-throughput experimentation was integral the discovery optimization both reactions. N-arylimines undergo formal (3+2) cycloaddition with yield azabicyclo[2.1.1]hexanes in a single step; contrast, N-alkylimines an addition/elimination sequence generate cyclobutenyl methanamine products high diastereoselectivity. These new contain variety synthetic handles for further elaboration, including many functional groups relevant pharmaceutical synthesis. reactivity observed attributed differences basicity nucleophilicity nitrogen atom common carbocation intermediate, leading either nucleophilic attack (N-aryl) or E1 elimination (N-alkyl).

Язык: Английский

Процитировано

143
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

141
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

127