Enantioselective dearomative ortho-cycloaddition transformation of inactive arenes by cage-confined photocatalysis DOI Creative Commons
Cheng‐Yong Su, Jie Yang,

X.‐M. WU

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 24, 2023

Abstract Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, asymmetric photocatalysis inactive remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined method for intramolecular dearomative cycloaddition electron-deficient β-aryl enones. Owing multi-functional synergy chirality, energy transfer, host-guest interactions confined microenvironments, self-assembled chiral cage-photoreactor could pre-organize activate enones give stereoselectively fused cyclobutanes through visible-light induced [2+2] ortho-cycloaddition. Notably, unavoidable transformation [4+2] cycloadducts has been inhibited, producing thermodynamically unfavorable with outstanding regio-, diastereo-, enantioselectivities.

Language: Английский

Enantioselective dearomative ortho-cycloaddition transformation of unactivated arenes by cage-confined visible-light photocatalysis DOI Creative Commons
Jie Yang, Zhongshu Li,

X.‐M. WU

et al.

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

Published: April 28, 2025

Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, asymmetric photocatalysis unactivated remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined visible-light method for intramolecular dearomative cycloaddition with electron-deficient β-aryl enones. Owing multi-functional synergy chirality, energy transfer, host-guest interactions confined microenvironments, self-assembled chiral cage-photoreactor could pre-organize activate enones give stereoselectively fused cyclobutanes through induced [2 + 2] ortho-cycloaddition. Notably, competing transformation [4 cycloadducts has been inhibited, producing thermodynamically unfavorable excellent regio-, diastereo-, enantioselectivities.

Language: Английский

Citations

0
Asymmetric Brominative Dearomatization of 2-Naphthols Using a Cinchona Alkaloid-Based Organocatalyst DOI

Kouhei Omae,

Yoshihiro Miyake, Mio Shimogaki

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4232 - 4236

Published: March 4, 2024

A cinchona alkaloid-based organocatalyst enables asymmetric brominative dearomatization of 2-naphthols, providing the corresponding bromonaphthalenones with high enantioselectivities. The first metal-free reaction can accommodate a variety functional groups and give useful frameworks bearing Br-containing tetrasubstituted stereogenic center.

Language: Английский

Citations

0
Systematic Studies of Functional Group Tolerance and Chemoselectivity in Carbene-Mediated Intramolecular Cyclopropanation and Intermolecular C–H Functionalization DOI Open Access

Haruki Kanda,

Ayaka Okabe,

Shingo Harada

et al.

Chemical and Pharmaceutical Bulletin, Journal Year: 2024, Volume and Issue: 72(3), P. 313 - 318

Published: March 15, 2024

Generating reliable data on functional group compatibility and chemoselectivity is essential for evaluating the practicality of chemical reactions predicting retrosynthetic routes. In this context, we performed systematic studies using a evaluation kit including 26 kinds additives to assess tolerance carbene-mediated reactions. Our findings revealed that some intermolecular heteroatom-hydrogen insertion proceed faster than intramolecular cyclopropanation Lewis basic functionalities inhibited rhodium-catalyzed C-H functionalization indoles. While performing these studies, observed an unexpected 1-naphthol variant used as additive.

Language: Английский

Citations

0
PIFA-Mediated Intramolecular Dearomatization of Phenol-Tethered 1,2-Diazoles: Synthesis of Spirocyclohexadienone Pyrazolo[3,4-b]piperidinones DOI
Pradeep Natarajan,

Pratibha Bachhaley,

S. K. Tripathy

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 8, 2024

Abstract In recent years, the significance of spirocyclic motifs in drug discovery has increased, owing to their unique ability engage biological targets. We present first example PIFA-mediated dearomative spirocyclization phenol-tethered pyrazoles, highlighting intramolecular trapping by pyrazole moiety. This method efficiently affords a variety spirocyclohexadienone-pyrazolo[3,4-b]piperidinones with yields up 82%. Mechanistic studies reveal that dearomatization process involves cationic intermediate.

Language: Английский

Citations

0
Atom-Efficient Chlorinative Dearomatization of Naphthol, Quinolinol, and Isoquinolinol Derivatives using Trichloroisocyanuric Acid (TCCA) DOI

Jenna D. Caudle,

Mary Ennis,

Dillon C. Dodge

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 30, 2024

A variety of dearomatized compounds have been prepared in moderate to excellent yields from planar scaffolds using trichloroisocyanuric acid (TCCA) as an atom-economical chlorinating agent. The method tolerates a broad range functionalities and can take place several green and/or sustainable solvents. Twenty-one examples 1,1-dichlorinated products 2-naphthols analogous heteroarenes (quinolinols, isoquinolinols, quinazolinol) are reported along with five monochlorinated products. utility the 1,1-dichloronaphthalenone product reactive intermediate species is demonstrated two-step, one-pot reaction carried out solvent. In mechanistic investigation, coordination agent hydroxy substituent scaffold prior chlorine transfer implicated.

Language: Английский

Citations

0
Enantioselective dearomative ortho-cycloaddition transformation of inactive arenes by cage-confined photocatalysis DOI Creative Commons
Cheng‐Yong Su, Jie Yang,

X.‐M. WU

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 24, 2023

Abstract Photoinduced dearomatization of arenes is a powerful strategy in organic synthesis to disrupt the stable aromaticity; however, asymmetric photocatalysis inactive remains highly challenging and rare. Herein we demonstrate an enzyme-mimicking cage-confined method for intramolecular dearomative cycloaddition electron-deficient β-aryl enones. Owing multi-functional synergy chirality, energy transfer, host-guest interactions confined microenvironments, self-assembled chiral cage-photoreactor could pre-organize activate enones give stereoselectively fused cyclobutanes through visible-light induced [2+2] ortho-cycloaddition. Notably, unavoidable transformation [4+2] cycloadducts has been inhibited, producing thermodynamically unfavorable with outstanding regio-, diastereo-, enantioselectivities.

Language: Английский

Citations

0