Dearomative Ring‐Fused Azafulleroids and Carbazole‐Derived Metallofullerenes: Reactivity Dictated by Encapsulation in a Fullerene Cage DOI
Tongxin Liu, Xin Wang,

Shilu Xia

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Oct. 4, 2023

Abstract Herein, we report divergent additions of 2,2′‐diazidobiphenyls to C 60 and Sc 3 N@I h ‐C 80 . In stark contrast that the previously reported bis‐azide additions, unexpected cascade reaction leads dearomative formation azafulleroids 2 fused with a 7‐6‐5‐membered ring system in case contrast, corresponding switches C−H insertion pathway, thereby resulting multiple isomers, including carbazole‐derived [6,6]‐azametallofulleroid [5,6]‐azametallofulleroid 4 an unusual 1,2,3,6‐tetrahydropyrrolo[3,2‐c]carbazole‐derived metallofullerene 5 , whose molecular structures have been unambiguously determined by single‐crystal X‐ray diffraction analyses. Among them, addition type is observed for first time all azides fullerenes. Furthermore, isomerizations from discovered, providing examples isomerization azafulleroid fullerene rather than aziridinofullerene. particular, isomerism [5,6]‐isomer unprecedented chemistry, contradicting present understanding generally occurs between [5,6]‐ [6,6]‐isomers. Control experiments carried out rationalize mechanism. representative applied organic solar cells, improved power conversion efficiencies.

Language: Английский

Rejuvenation of dearomative cycloaddition reactions via visible light energy transfer catalysis DOI Creative Commons

Angshuman Palai,

Pramod Rai,

Biplab Maji

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(43), P. 12004 - 12025

Published: Jan. 1, 2023

Dearomative cycloaddition is a powerful technique to access sp

Language: Английский

Citations

34
Oxidative Dearomatization of Pyridines DOI

Zohaib Siddiqi,

Tanner W. Bingham, Tsukasa Shimakawa

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2358 - 2363

Published: Jan. 17, 2024

Dearomatization of pyridines is a well-established synthetic approach to access piperidines. Although remarkably powerful, existing dearomatization processes have been limited the hydrogenation or addition carbon-based nucleophiles activated pyridiniums. Here, we show that arenophile-mediated dearomatizations can be applied directly introduce heteroatom functionalities without prior substrate activation. The arenophile platform in combination with olefin oxidation chemistry provides dihydropyridine cis-diols and epoxides. These previously elusive compounds are now readily accessible used for downstream preparation diversely functionalized

Language: Английский

Citations

15
Photochemical dearomative skeletal modifications of heteroaromatics DOI Creative Commons
Peng Ji, Kuaikuai Duan, Menglong Li

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(12), P. 6600 - 6624

Published: Jan. 1, 2024

Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.

Language: Английский

Citations

13
Visible photons as ideal reagents for the activation of coloured organic compounds DOI Creative Commons
Lorenzo Di Terlizzi, Luca Nicchio,

Stefano Protti

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Language: Английский

Citations

11
Photo-induced intramolecular dearomative [5 + 4] cycloaddition of arenes for the construction of highly strained medium-sized-rings DOI Creative Commons
Min Zhu, Yuanjun Gao,

Xu‐Lun Huang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 19, 2024

Abstract Medium-sized-ring compounds have been recognized as challenging synthetic targets in organic chemistry. Especially, the difficulty of synthesis will be augmented if an E -olefin moiety is embedded. Recently, photo-induced dearomative cycloaddition reactions that proceed via energy transfer mechanism witnessed significant developments and provided powerful methods for transformations are not easily realized under thermal conditions. Herein, we report intramolecular [5 + 4] naphthalene-derived vinylcyclopropanes visible-light irradiation a proper triplet photosensitizer. The reaction affords dearomatized polycyclic molecules possessing nine-membered-ring with good yields (up to 86%) stereoselectivity 8.8/1 / Z ). Detailed computational studies reveal origin behind favorable formation thermodynamically less stable isomers. Diverse derivations products also demonstrated.

Language: Английский

Citations

10
Skeletal Transformation of Unactivated Arenes Enabled by a Low-Temperature Dearomative (3 + 2) Cycloaddition DOI
Sajan Pradhan, Fahimeh Mohammadi, Jean Bouffard

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12214 - 12223

Published: May 24, 2023

Simple aromatic compounds like benzene are abundant feedstocks, for which the preparation of derivatives chiefly begins with electrophilic substitution reactions or, less frequently, reductions. Their high stability makes them particularly reluctant to participate in cycloadditions under ordinary reaction conditions. Here, we demonstrate exceptional ability 1,3-diaza-2-azoniaallene cations undergo formal (3 + 2) unactivated below room temperature, providing thermally stable dearomatized adducts on a multi-gram scale. The cycloaddition, tolerates polar functional groups, activates ring toward further elaboration. On treatment dienophiles, cycloadducts (4 cycloaddition–cycloreversion cascade yield substituted or fused arenes, including naphthalene derivatives. overall sequence results transmutation arenes through an exchange carbons: two-carbon fragment from original is replaced another incoming dienophile, introducing unconventional disconnection synthesis ubiquitous building blocks. Applications this two-step acenes, isotopically labeled molecules, and medicinally relevant demonstrated.

Language: Английский

Citations

18
Transition metal complexes: A new era of photosensitizers for Dearomative photocycloaddition/annulation via energy and Electron transfer Photocatalysis DOI

Ram Narayan Yadav,

Ashok Srivastava, Sovan Dey

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 520, P. 216136 - 216136

Published: Aug. 14, 2024

Language: Английский

Citations

7
Copper‐Catalyzed Dearomative 1,2‐Hydroamination DOI Creative Commons
Christopher William Davis, Yu Zhang, Yanrong Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 23, 2024

Catalytic olefin hydroamination reactions are some of the most atom-economical transformations that bridge readily available starting materials-olefins and high-value-added amines. Despite significant advances in this field over last two decades, formal nonactivated aromatic compounds remains an unsolved challenge. Herein, we report extension to π-systems by using arenophile-mediated dearomatization Cu-catalysis perform 1,2-hydroamination on arenes. This strategy was applied a variety substituted arenes heteroarenes provide general access structurally complex We conducted DFT calculations inform mechanistic understanding rationalize unexpected selectivity trends. Furthermore, developed practical, scalable desymmetrization deliver enantioenriched dearomatized products enable downstream synthetic applications. ultimately used dearomative efficiently synthesize collection densely functionalized small molecules.

Language: Английский

Citations

6
A Dual Cobalt‐Photoredox Catalytic Approach for Asymmetric Dearomatization of Indoles with Aryl Amides via C−H Activation DOI

Abir Das,

Subramani Kumaran,

Harihara Subramanian Ravi Sankar

et al.

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

Published: June 19, 2024

Abstract In this study, we unveil a novel method for the asymmetric dearomatization of indoles under cobalt/photoredox catalysis. By strategically activating C−H bonds amides and subsequent migratory insertion π‐bonds present in indole as reactive partner, achieve syn ‐selective tetrahydro‐5 H ‐indolo[2,3‐ c ]isoquinolin‐5‐one derivatives with excellent yields enantiomeric excesses up to >99 %. The developed operates without metal oxidant, relying solely on oxygen oxidant employing an organic dye photocatalyst irradiation. Control experiments stoichiometric studies elucidate reversible nature enantiodetermining activation step, albeit not being rate‐determining. This study only expands horizon cobalt‐catalyzed bond functionalization, but also showcases potential synergy between cobalt photoredox catalysis enabling synthesis complex molecules.

Language: Английский

Citations

4
Copper-Catalyzed Dearomative trans-1,2-Carboamination DOI
C.W. Davis, Yanrong Li, Yu Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 10132 - 10137

Published: June 20, 2024

We have achieved the arenophile-mediated, copper-catalyzed dearomative trans-1,2-carboamination of nonactivated arenes with alkyl organometallic nucleophiles. This simple and practical procedure was used to prepare diverse, stereochemically rich alkylated cyclohexadienes from readily available arenes. Synthetic utility demonstrated through rapid preparation complex small molecules difficult access by conventional routes. Finally, we conducted DFT studies explore catalytic process, including a study reaction pathway an examination divergent regioselectivity observed substituted

Language: Английский

Citations

4