High pressure promoted dearomatization of nitroarenes by [4+2] cycloadditions with silyloxydienes

Rkein, Batoul; Coffinier, Romain; Powderly, Marian; Manneveau, Maxime; Sanselme, Morgane; Durandetti, Muriel; Sebban, Muriel; Hamdoun, Ghanem; Oulyadi, Hassan; Harrowven, David C.; Legros, Julien; Chataigner, Isabelle

doi:10.1039/d2cc04778k

Cited by 5 publications

(9 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast, a tetracyclic bis‐cycloadduct 7 a was formed from 1,3‐dinitronaphthalene (95 %), arising from a bis‐cycloaddition process. These results are in line with our previous observations in Diels–Alder reactions [31] . Changing dipole was possible and the use of the N ‐methylated hemiaminal ether precursor led to the efficient formation bis‐cycloadduct 7 b in a good 72 % yield.…”

Section: Resultssupporting

confidence: 92%

“…In the development of greener processes, not only the technology (such as photochemistry) plays an important role but also the chemicals, among which the solvent represents ‐by far‐ the biggest part [31–33] . Whereas acetonitrile can be tolerated as polar aprotic solvent, its substitution by ethyl acetate is desirable [32] .…”

Section: Resultsmentioning

confidence: 99%

“…These results are in line with our previous observations in Diels-Alder reactions. [31] Changing dipole was possible and the use of the N-methylated hemiaminal ether precursor led to the efficient formation bis-cycloadduct 7 b in a good 72 % yield. Similarly, 1,3-dinitrobenzene afforded a cycloadduct resulting from a double reaction, 8 a, isolated in 75 % yield, in a longer residence time (t R = 40 min) for this more aromatic arene.…”

Section: Homogeneous Conditionsmentioning

confidence: 99%

“…In the development of greener processes, not only the technology (such as photochemistry) plays an important role but also the chemicals, among which the solvent represents -by far-the biggest part. [31][32][33] Whereas acetonitrile can be tolerated as polar aprotic solvent, its substitution by ethyl acetate is desirable. [32] Therefore, whereas previous reactions were performed on 0.2 mmol scale of aromatic compound in MeCN, we now assessed the dearomatization of 1,3-dinitronaphthalene on a 4 mmol scale in AcOEt (Scheme 2).…”

Section: Homogeneous Conditionsmentioning

confidence: 99%

See 3 more Smart Citations

Photocatalyzed (3+2) Cycloaddition for the Dearomatization of Electron‐Poor Arenes under Flow Conditions

Faye,

Rkein,

Bigot

et al. 2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Dedicated to Dr. Jean-Pierre Bégué on the occasion of his 85 th birthday.The photocatalyzed dearomative reaction between various electron-deficient aromatic compounds and a non-stabilized azomethine ylide is successfully performed in a flow system. Whereas the use of supported eosin as organic photocatalyst exhibits limited efficiency, turning to the soluble Rose Bengal allows to transform a broad range of substrates from hetarenes (indole, benzofuran, quinoline, pyridine) to naphthalenes and benzenes. This photocatalyzed (3 + 2) dearomative cycloaddition under green light irradiation provides a simple and efficient access to tridimensional pyrrolidino scaffolds with a tetrasubstituted carbon center at ring junction and can be performed in the friendly ethyl acetate. Computational studies support the mechanism involving azomethine ylide as reactive species toward the electron-poor arene.

show abstract

Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Homogeneous Conditionsmentioning

confidence: 99%

Section: Homogeneous Conditionsmentioning

confidence: 99%

See 2 more Smart Citations

Photocatalyzed (3+2) Cycloaddition for the Dearomatization of Electron‐Poor Arenes under Flow Conditions

Faye,

Rkein,

Bigot

et al. 2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…The last work within this section was recently accomplished by Chataigner and co-workers and it dealed with the dearomatization of 5-nitro(iso)quinolines acting as dienophiles in (4 + 2) cycloaddition reactions with silyloxydienes 223 under high pressure, without thermal or chemical activation ( Scheme 107 ). 165 The process took place at room temperature and produced the dearomatization of the arene moiety. After hydrolysis of the silylenol ether, polycyclic scaffolds 224 were obtained with complete regioselectivity, in good yields, as nearly equimolecular mixtures of diastereoisomers at the methoxy-containing stereocenter.…”

Section: Cycloaddition Reactions and Annulationsmentioning

confidence: 99%

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Escolano,

Gaviña,

Alzuet-Piña

et al. 2024

Chem. Rev.

View full text Add to dashboard Cite

Dearomatization reactions have become fundamental chemical transformations in organic synthesis since they allow for the generation of three-dimensional complexity from two-dimensional precursors, bridging arene feedstocks with alicyclic structures. When those processes are applied to pyridines, quinolines, and isoquinolines, partially or fully saturated nitrogen heterocycles are formed, which are among the most significant structural components of pharmaceuticals and natural products. The inherent challenge of those transformations lies in the low reactivity of heteroaromatic substrates, which makes the dearomatization process thermodynamically unfavorable. Usually, connecting the dearomatization event to the irreversible formation of a strong C−C, C− H, or C−heteroatom bond compensates the energy required to disrupt the aromaticity. This aromaticity breakup normally results in a 1,2-or 1,4-functionalization of the heterocycle. Moreover, the combination of these dearomatization processes with subsequent transformations in tandem or stepwise protocols allows for multiple heterocycle functionalizations, giving access to complex molecular skeletons. The aim of this review, which covers the period from 2016 to 2022, is to update the state of the art of nucleophilic dearomatizations of pyridines, quinolines, and isoquinolines, showing the extraordinary ability of the dearomative methodology in organic synthesis and indicating their limitations and future trends.

show abstract

Controlling Diastereoselectivity in Dearomatizing Diels‐Alder Reactions of Nitroarenes with 2‐Trimethylsilyloxycyclohexadiene

Powderly,

Roseau,

Frison

et al. 2024

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Dearomative Diels‐Alder cycloadditions between nitroarenes and 2‐trimethylsilyloxycyclohexadiene are carried out under high pressure at room temperature in the absence of any chemical promoter. Reactions are performed with different arenes, including the highly aromatic naphthalenes and quinolines. They lead to 3D‐scaffolds with exquisite exo‐diastereoselectivity. The exo approach is characterized by lower distortion of the substrates in a late TS and by more favorable orbital interactions presumably between the nitro group and the dienic part, explaining the stereoselectivity

show abstract

High pressure promoted dearomatization of nitroarenes by [4+2] cycloadditions with silyloxydienes

Abstract: Simple nitroarenes such as nitronaphthalenes and nitroquinolines smoothly undergo dearomatizing [4+2] cycloadditions with silyloxydienes under 16 kbar. Highly functionalized 3-dimensional polycyclic adducts bearing a tetrasubstituted carbon centre at the ring...

Cited by 5 publications

References 44 publications

Photocatalyzed (3+2) Cycloaddition for the Dearomatization of Electron‐Poor Arenes under Flow Conditions

Photocatalyzed (3+2) Cycloaddition for the Dearomatization of Electron‐Poor Arenes under Flow Conditions

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Controlling Diastereoselectivity in Dearomatizing Diels‐Alder Reactions of Nitroarenes with 2‐Trimethylsilyloxycyclohexadiene

Contact Info

Product

Resources

About