EDA Complex from BCP‐Thianthrenium Salt: A Catalyst‐free Strategy To Access 1‐Trifluoromethyl‐3‐quinoxaline Derivatives Bicyclo[1.1.1]pentanes DOI
Guofu Zhang, Zijin Luo,

Guangyao Mei

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(27)

Published: May 13, 2024

Abstract The construction of bicyclo[1.1.1.]pentanes (BCPs) typically require the cumbersome use labile [1.1.1.]propellane in solution and involve multicomponent radical reactions, which commonly produce undesired by‐products that hinder efficient BCPs. In this paper, we present a catalyst‐free strategy by constructing an electron donor‐acceptor (EDA) complex utilizing naturally electron‐deficient nature BCP thianthrenium salt, were irradiated with visible light to obtain trifluoromethyl‐BCP radicals through SET process, subsequently reacted various substituted quinoxalines. Moreover, successful structural modification drug molecule derivatives confirm utility scheme field discovery.

Language: Английский

A General and Modular Approach to BCP Alkylamines via Multicomponent Difunctionalization of [1.1.1]Propellane DOI
Weichen Huang, Yongxiang Zheng, Sebastian Keeß

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 5363 - 5369

Published: Feb. 21, 2023

Over the past decade, bicyclo[1.1.1]pentane (BCP) motifs have come to fore as valuable pharmaceutical bioisosteres of para-disubstituted benzenes. However, limited approaches and requisite multistep syntheses useful BCP building blocks are hampering early discovery research in medicinal chemistry. Herein we report development a modular strategy for divergent preparation functionalized alkylamines. In this process, general method introduce fluoroalkyl groups scaffolds using readily available easy-to-handle sulfinate salts was also developed. Moreover, can be extended S-centered radicals incorporation sulfones thioethers into core. Overall, multicomponent enables rapid construction BCP-type applications drug discovery.

Language: Английский

Citations

56
Light‐Driven Synthesis and Functionalization of Bicycloalkanes, Cubanes and Related Bioisosteres DOI Creative Commons
Sara Cuadros, Julien Paut, Elsa Anselmi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Jan. 5, 2024

Bicycloalkanes, cubanes and their structural analogues have emerged as bioisosteres of (hetero)arenes. To meet increasing demand, the chemical community has developed a plethora novel synthetic methods. In this review, we assess progress made in field light-driven construction functionalization such relevant molecules. We focused on diverse targets, well reaction processes giving access to: (i) [1.1.1]-bicyclopentanes (BCPs); (ii) [2.2.1]-bicyclohexanes (BCHs); (iii) [3.1.1]-bicycloheptanes (BCHeps); (iv) cubanes; other structurally related scaffolds. Finally, future perspectives dealing with identification manifolds to new functionalized bioisosteric units are discussed.

Language: Английский

Citations

28
Strain-release transformations of bicyclo[1.1.0]butanes and [1.1.1]propellanes DOI Creative Commons
Qianqian Hu, Jie Chen, Yang Yang

et al.

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 9, P. 100070 - 100070

Published: Feb. 28, 2024

Bicyclo[1.1.0]butanes (BCBs) and [1.1.1]propellanes (tricyclo[1.1.1.01,3]pentanes, TCPs) are structurally unique compounds with different chemical properties. Strain-release driven reactions have emerged as an atom- step-economic strategy for the organic synthesis. Using this strategy, a variety of functional ring molecules been efficiently synthesized, including various cyclobutane molecules, bicyclo[2.1.1]hexanes, bicyclo[1.1.1]pentanes, others. More specifically, these strain release-driven include aspects nucleophilic addition, radical electrophilic or transition metal catalysis. This review will discuss recent developments in strain-release transformations bicyclo[1.1.0]butanes [1.1.1]propellanes.

Language: Английский

Citations

27
Synthesis of 1-perfluoroalkyl-3-heteroaryl bicyclo[1.1.1]pentanes via visible light-induced and metal-free perfluoroalkylation of [1.1.1]propellane DOI

Boan Yan,

Gongcheng Xu,

Hang Han

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(5), P. 1948 - 1954

Published: Jan. 1, 2023

Visible light-induced perfluoroalkylation of [1.1.1]propellane provides a sustainable way to incorporate perfluoroalkyl-substituted BCPs into various heterocycles.

Language: Английский

Citations

37
A General and Practical Route to Functionalized Bicyclo[1.1.1]Pentane‐Heteroaryls Enabled by Photocatalytic Multicomponent Heteroarylation of [1.1.1]Propellane DOI
Weichen Huang, Sebastian Keeß,

Gary A. Molander

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 15, 2023

Abstract 1‐Aryl‐substituted bicyclo[1.1.1]pentanes (BCPs) are an important class of BCP derivatives with widespread application in drug development. Most syntheses these materials require multiple chemical steps via electrophiles or nucleophiles derived from [1.1.1]propellane. Although one‐step, multicomponent radical cross‐coupling reactions could provide a more sustainable and rapid route to access diverse heteroarylated BCPs, current approaches limited tertiary alkyl radicals, leading decrease their practical value. In this study, conceptually different approach enabled by heteroarylation [1.1.1]propellane functionalized BCPs is described. Importantly, protocol compatible primary‐, secondary‐, aliphatic as well various fluoroalkyl sources, thus enabling library generation sought‐after for

Language: Английский

Citations

37
Electrochemical chemo- and regioselective arylalkylation, dialkylation and hydro(deutero)alkylation of 1,3-enynes DOI
Chen Zhu, Haifeng Chen, Huifeng Yue

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1068 - 1081

Published: June 22, 2023

Language: Английский

Citations

34
Visible light-induced synthesis of 1,3-disubstituted bicyclo[1.1.1]pentane ketonesviacooperative photoredox and N-heterocyclic carbene catalysis DOI
Yan Gao,

Zicong Zheng,

Yu Zhu

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 3909 - 3915

Published: Jan. 1, 2023

Visible light-induced highly efficient synthesis of 1,3-disubstituted bicyclo[1.1.1]pentane with mild conditions, high atom economy, and superior functional group tolerance.

Language: Английский

Citations

26
Photoinduced C(sp3)−H Bicyclopentylation Enabled by an Electron Donor–Acceptor Complex‐Mediated Chemoselective Three‐Component Radical Relay DOI

Xiaobo Dang,

Zhixuan Li,

Jinlong Shang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: April 10, 2024

The photoredox electron donor-acceptor (EDA) complex-mediated radical coupling reaction has gained prominence in the field of organic synthesis, finding widespread application two-component reactions. However, EDA complex-promoted multi-component reactions are not well developed with only a limited number examples have been reported. Herein, we report photoinduced and highly chemoselective three-component arylalkylation [1.1.1]propellane, which allows direct functionalization C(sp

Language: Английский

Citations

13
Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

Citations

12
Metal- and photocatalyst-free three-component strategy to prepare benzylalcohol-, aldehyde-substituted BCP building blocks DOI
Fei Li,

Huijuan Liao,

Jianyang Dong

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(9), P. 5531 - 5537

Published: Jan. 1, 2024

A mild one-step, light-promoted, three-component radical-coupling reaction of [1.1.1]propellane to afford difunctionalized benzylalcohol-, aldehyde-substituted BCPs in the absence metals, photocatalysts or external oxidants was reported.

Language: Английский

Citations

10