1.3 Synthesis of Small Fluorinated Carbocycles DOI
Lauriane C. Peyrical, André B. Charette

Published: Jan. 1, 2024

Abstract Small carbocycles, such as three- and four-membered rings, are highly strained motifs that represent an interesting class of organic compounds. Fluorinated analogs these scaffolds, combining the attractive features both small carbocycles fluorinated groups, have been studied for several decades, particularly in field medicinal chemistry. In recent years, achievements new developments reported synthesis carbocycles. particular, various substituents found increasing significance, fluoromethyl group (CFH2), difluoromethyl (CF2H), trifluoromethyl (CF3), pentafluorosulfanyl (SF5) group. Reviewed herein synthetic strategies developed between 2017 2024 to afford rings with emerging substituents.

Language: Английский

Radical Reactions in Organic Synthesis: Exploring in-, on-, and with-Water Methods DOI Creative Commons
Chryssostomos Chatgilialoglu, Sebastián Barata‐Vallejo, Thanasis Gimisis

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(3), P. 569 - 569

Published: Jan. 23, 2024

Radical reactions in water or aqueous media are important for organic synthesis, realizing high-yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to chemistry media, (ii) synthetic approaches in, on, with as well heterogeneous phases, (iii) of carbon-centered radicals (or deuterium oxide) activated through coordination various Lewis acids, (iv) photocatalysis (v) applications bioinspired by naturally occurring processes. A wide range chemical strategies different experimental conditions have been reviewed that lead functional group translocation transformation reactions, leading the preparation complex molecules. These results reveal how solvent/medium/reagent radical has matured over last two decades, further discoveries anticipated near future.

Language: Английский

Citations

8
Synthesis of cyclobutane-fused chromanones via gold-mediated photocatalysis DOI Creative Commons
Vladislav A. Voloshkin, Marco Villa, Ekaterina A. Martynova

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(12), P. 4571 - 4580

Published: Jan. 1, 2024

Energy transfer (EnT) photocatalysis has emerged as a valuable tool for constructing complex organic scaffolds

Language: Английский

Citations

6
Dearomative Construction of 2D/3D Frameworks from Quinolines via Nucleophilic Addition/Borate‐Mediated Photocycloaddition DOI

Asuha Shimose,

Shiho Ishigaki,

Yu Sato

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: May 28, 2024

Dearomative construction of multiply-fused 2D/3D frameworks, composed aromatic two-dimensional (2D) rings and saturated three-dimensional (3D) rings, from readily available quinolines has greatly contributed to drug discovery. However, dearomative cycloadditions in the presence photocatalysts usually afford 5,6,7,8-tetrahydroquinoline (THQ)-based polycycles, access 1,2,3,4-THQ-based structures remains limited. Herein, we present a chemo-, regio-, diastereo-, enantioselective transformation into 6-6-4-membered without any catalyst, through combination nucleophilic addition borate-mediated [2+2] photocycloaddition. Detailed mechanistic studies revealed that photoexcited borate complex, generated quinoline, organolithium, HB(pin), accelerates cycloaddition suppresses rearomatization occurs conventional Based on our analysis, also developed further photoinduced affording other types frameworks isoquinoline phenanthrene.

Language: Английский

Citations

6
Fluorine‐Effect‐Enabled Photocatalytic 4‐Exo‐Trig Cyclization Cascade to Access Fluoroalkylated Cyclobutanes DOI
Yulu Zhou, Zhenhua Wu, Jinming Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 13, 2024

Abstract Cyclobutanes are popular structural units in bioactive compounds and versatile intermediates synthetic chemistry, but their synthesis is challenging owing to high ring strain. In this study, a novel method for highly regio‐ diastereoselective of fluoroalkylcyclobutanes bearing vicinal quaternary tertiary stereocenters realized by photocatalytic 4‐exo‐trig cyclization cascade thioalkynes or trifluoromethylalkenes. Density functional theory calculations reveal that unique fluorine effect, arising from hyperconjugative π→σ* C‐F interactions, accounts the regio‐reversed radical addition at sterically hindered alkene carbon, which facilitates an unprecedented closure. This chemistry enables direct controllable construction medicinally valuable quaternary‐carbon‐containing cyclobutanes readily available raw materials, nicely complementing existing methods.

Language: Английский

Citations

4
Visible Light-Induced Regioselective Intermolecular [2 + 2]-Cycloaddition of Alkyne and 2(1H)-Quinolone Derivatives DOI
Hai Hao,

Shaoheng Qin,

Yanzhi Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 1353 - 1360

Published: Jan. 8, 2024

We have developed a visible light-induced intermolecular [2 + 2]-cycloaddition reaction between alkenes and alkynes using thioxanthone Cu(OTf)2 as cocatalysts. Various quinolin-2(1H)-ones, featuring diverse substituted groups, were successfully employed in this reaction, resulting the synthesis of series 4,8b-dihydrocyclobuta[c]quinolin-3(2aH)-ones. Our methodology presents novel synthetic approach for alkene-alkyne 2]-cycloaddition, delivering cyclobutene derivatives with exceptional regioselectivity.

Language: Английский

Citations

2
Creation of a Chiral All-Carbon Quaternary Center Induced by CF3 and CH3 Substituents via Cu-Catalyzed Asymmetric Conjugate Addition DOI Creative Commons

Taiyo Yamamoto,

Masayuki Asakura,

Ken Yamanomoto

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5312 - 5317

Published: June 13, 2024

Cu-catalyzed asymmetric construction of a chiral quaternary center bearing CH3 and CF3 groups was achieved with high to excellent enantioselectivity using our originally developed ligands. The conjugate addition Me3Al β-CF3-substituted enones unsaturated ketoesters proceeded efficiently. use gives optically active furanones in yields enantioselectivities. perfluoroalkyl-substituted enone does not seem be favorable the present reaction.

Language: Английский

Citations

2
CF3-Cyclobutanes: Synthesis, Properties, and Evaluation as a Unique tert-Butyl Group Analogue DOI Creative Commons

Volodymyr Ahunovych,

Anton A. Klipkov, Maksym Ya. Bugera

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(11), P. 4507 - 4517

Published: Nov. 11, 2024

Isosteric replacement of functional groups is an emerging strategy for optimizing bioactive molecules in drug discovery.

Language: Английский

Citations

1
Halogen-bond-assisted radical remote difunctionalization of bicyclo[1.1.1]butane skeleton DOI
Hui Liu, Zhenda Fu, Xingwei Li

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Transition-metal-free radical remote difunctionalization of bicyclo[1.1.1]butane skeletons in both two- and three-component fashions is presented.

Language: Английский

Citations

1
Fluorine‐Effect‐Enabled Photocatalytic 4‐Exo‐Trig Cyclization Cascade to Access Fluoroalkylated Cyclobutanes DOI
Yulu Zhou, Zhenzhen Wu, Jinming Xu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 13, 2024

Abstract Cyclobutanes are popular structural units in bioactive compounds and versatile intermediates synthetic chemistry, but their synthesis is challenging owing to high ring strain. In this study, a novel method for highly regio‐ diastereoselective of fluoroalkylcyclobutanes bearing vicinal quaternary tertiary stereocenters realized by photocatalytic 4‐exo‐trig cyclization cascade thioalkynes or trifluoromethylalkenes. Density functional theory calculations reveal that unique fluorine effect, arising from hyperconjugative π→σ* C‐F interactions, accounts the regio‐reversed radical addition at sterically hindered alkene carbon, which facilitates an unprecedented closure. This chemistry enables direct controllable construction medicinally valuable quaternary‐carbon‐containing cyclobutanes readily available raw materials, nicely complementing existing methods.

Language: Английский

Citations

0
Dearomative Construction of 2D/3D Frameworks from Quinolines via Nucleophilic Addition/Borate‐Mediated Photocycloaddition DOI

Asuha Shimose,

Shiho Ishigaki,

Yu Sato

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: May 28, 2024

Abstract Dearomative construction of multiply‐fused 2D/3D frameworks, composed aromatic two‐dimensional (2D) rings and saturated three‐dimensional (3D) rings, from readily available quinolines has greatly contributed to drug discovery. However, dearomative cycloadditions in the presence photocatalysts usually afford 5,6,7,8‐tetrahydroquinoline (THQ)‐based polycycles, access 1,2,3,4‐THQ‐based structures remains limited. Herein, we present a chemo‐, regio‐, diastereo‐, enantioselective transformation into 6–6–4‐membered without any catalyst, through combination nucleophilic addition borate‐mediated [2+2] photocycloaddition. Detailed mechanistic studies revealed that photoexcited borate complex, generated quinoline, organolithium, HB(pin), accelerates cycloaddition suppresses rearomatization occurs conventional Based on our analysis, also developed further photoinduced affording other types frameworks isoquinoline phenanthrene.

Language: Английский

Citations

0