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

Light‐Induced Domino and Multicomponent Reactions: How to Reach Molecular Complexity without a Catalyst DOI Creative Commons
Polyssena Renzi, Jacopo Scarfiello, Alberto Lanfranco

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: unknown

Published: Aug. 31, 2023

Abstract Achieving high molecular complexity can be not trivial, but the exploitation of domino reactions provides an atom‐ and step‐economical method to reach this target. Over past decades, a lot efforts have been put on development photocatalytic cascades employing both metal‐based purely organic catalysts. Despite effectiveness these protocols, catalyst‐ additive‐free light‐induced are gaining momentum thank their efficiency, operational simplicity sustainability. The increasing number papers published field in last years is proof appeal transformations. In Review, we discuss multicomponent mediated by light with focus photocatalyst‐ processes. most recent advances synthesis complex nitrogen‐, oxygen‐, sulphur‐ selenium‐heterocycles together analysed emphasis experimental mechanistic studies.

Language: Английский

Citations

10
Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C–H Alkylation of Allylic Alcohols DOI
Yusuke Kuroda, Takashi Chiba,

Moe Kawajiri

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

We present a protocol for regioselective allylic C-H alkylation of alcohols, consisting sequential azo-ene reaction and attendant Pd-catalyzed substitution with Grignard reagents. Notable features this work include: (1) C(sp3)-C(sp3) bond formation is achieved under Pd-catalysis, (2) the proceeds retention configuration at electrophilic carbon as well olefin geometry.

Language: Английский

Citations

0
Photoinduced Dearomative Multiple Functionalization of Quinolines to Construct Highly Substituted 3D Frameworks DOI
Yuki Nagashima,

Asuha Shimose

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

Abstract Dearomative functionalization of quinolines expands the chemical diversity highly functionalized 3D frameworks, such as 1,2,3,4- and 5,6,7,8-tetrahydroquinoline derivatives, which are important pharmacophores, with minimal synthetic costs. In this short review, we cover recent reports on visible-light-induced dearomative an emphasis reaction design/strategies mechanistic studies provide a theoretical basis for developing further syntheses in future. 1 Introduction 2 Functionalizations through Formation Photoexcited Quinolines 3 Reagents/Intermediates 4 Conclusion

Language: Английский

Citations

0
Reimagining Dearomatization: Arenophile-Mediated Single-Atom Insertions and π-Extensions DOI

Zohaib Siddiqi,

David Šarlah

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

ConspectusDearomatization of simple aromatics serves as one the most direct strategies for converting abundant chemical feedstocks into three-dimensional value-added products. Among such transformations, cycloadditions between arenes and alkenes have historically offered effective means to construct complex polycyclic architectures. However, traditionally harsh conditions, high-energy UV light irradiation, greatly limited scope this transformation. Nevertheless, recent progress has led development visible-light-promoted dearomative photocycloadditions with expanded capable preparing bicyclic structures.A fundamentally distinct approach involves visible-light activation arenophiles, which undergo para-photocycloaddition various aromatic compounds produce arene-arenophile cycloadducts. While only transiently stable subject retro-cycloaddition, further functionalization photocycloadducts allowed a wide collection dearomatization methodologies that access products orthogonal existing biological processes. Central strategy was observation photocycloaddition reveals π-system can be functionalized through traditional olefin chemistry. Coupled subsequent [4 + 2]-cycloreversion arenophile, process acts effectively isolate single from an ring. We developed several transformations bias methodology perform single-atom insertion π-extension reactions prepare unique cannot prepared easily means.Through application epoxidation, we were able develop method epoxidation pyridines arene-oxides pyridine-oxides, respectively. Notably, when arenophile chemistry is applied arenes, transposed site native olefinic reactivity, enabling site-selectivity functionalization. As result, oxygen (aza)arenes 3-benzoxepines. When applying in context cyclopropanations, accomplish cyclopropanation yield benzocycloheptatrienes upon cycloreversion. while Buchner ring expansion powerful carbon corresponding does not ring-expanded Furthermore, could utilized synthesis novel nanographenes M-region annulative (M-APEX) reaction. Traditionally, methods rely on reactivity at K- bay-region. arenophiles activate reactivity. arenophile-mediated diarylation, followed by cycloreversion, deliver π-extended exclusive selectivity.

Language: Английский

Citations

0
4.1 Arenophile-Mediated Photochemical Dearomative Functionalization DOI
Mitchio Okumura

Published: Jan. 1, 2025

Abstract Dearomatizations have long been recognized as an important class of reactions, with significant progress achieved; however, the utilization simple and nonactivated arenes remains a challenging endeavor due to their inherent inertness difficulty achieving selective transformations. This review highlights emerging dearomatization approach that enables conversion such under mild conditions: arenophile-mediated photochemical dearomative functionalization. methodology provides efficient access alicyclic structures, offering both functional stereochemical complexity, including C—C, C—B, C—N, C—O, C—H bond formations. Applications in synthesis complex bioactive compounds are also presented demonstrate unique versatility this strategy.

Language: Английский

Citations

0
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 International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 4, 2023

Herein, we report divergent additions of 2,2'-diazidobiphenyls to C60 and Sc3 N@Ih -C80 . 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 3 [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 5 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

Citations

7
Synthesis of mesoionic triazolones via a formal [3+2] cycloaddition between 4-phenyl-1,2,4-triazoline-3,5-dione and alkynes DOI
Yusuke Kuroda,

Maya Krell,

Kazuma Kurokawa

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(13), P. 1719 - 1722

Published: Jan. 1, 2024

1,2,4-Triazoline-3,5-diones (TADs) are versatile reagents and have found widespread adoption in chemical science.

Language: Английский

Citations

0
Copper‐Catalyzed Dearomative 1,2‐Hydroamination DOI Creative Commons
Christopher William Davis, Yu Zhang, Yanrong Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 23, 2024

Abstract 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

0
Dearomative Intramolecular meta‐Thermocycloadditions of Benzene Rings via Wheland Intermediates DOI
Shupeng Liu, Tianyi Xu, Yuting Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(35)

Published: June 5, 2024

Abstract Dearomative cycloadditions are powerful synthetic transformations utilizing aromatic compounds for cycloaddition reactions. They have been extensively applied to the synthesis of biologically relevant not only because complexity generated from simplicity but also atom‐ and step‐economy. For most studied yet challenging benzene ring systems, ortho ‐ para ‐cycloadditions realized both photochemically thermally, while meta still limited photochemical processes tracing back 1960s. Herein, we first time thermal rings with alkenes in a fashion via Wheland intermediates. A broad spectrum readily available C(sp 2 )‐rich aniline‐tethered enynes were transformed into 3 3D complex polycyclic architectures simply by stirring TFA. Moreover, reaction could be performed gram‐scales products diversely elaborated.

Language: Английский

Citations

0
Dearomative Intramolecular meta‐Thermocycloadditions of Benzene Rings via Wheland Intermediates DOI
Shupeng Liu, Tianyi Xu, Yuting Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: June 5, 2024

Abstract Dearomative cycloadditions are powerful synthetic transformations utilizing aromatic compounds for cycloaddition reactions. They have been extensively applied to the synthesis of biologically relevant not only because complexity generated from simplicity but also atom‐ and step‐economy. For most studied yet challenging benzene ring systems, ortho ‐ para ‐cycloadditions realized both photochemically thermally, while meta still limited photochemical processes tracing back 1960s. Herein, we first time thermal rings with alkenes in a fashion via Wheland intermediates. A broad spectrum readily available C(sp 2 )‐rich aniline‐tethered enynes were transformed into 3 3D complex polycyclic architectures simply by stirring TFA. Moreover, reaction could be performed gram‐scales products diversely elaborated.

Language: Английский

Citations

0