Synthesis of Chiral Diazocine Derivatives via a Copper-Catalyzed Dearomative [5+3] Cycloaddition

Lee, Ju Young; Varshnaya, Rohit Kumar; Yoo, Eun Jeong

doi:10.1021/acs.orglett.2c01389

Cited by 14 publications

(5 citation statements)

References 30 publications

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“…Very recently, the same authors found that copper(I) chloride catalyzed an enantioselective (5 + 3) cycloaddition of quinolinium zwitterions 131 and enol diazoacetates 122 in the presence of a sterically encumbered chiral BOX-type ligand and NaBArF as a crucial additive (Scheme ). In this manner, enantioenriched diazocine derivatives 147 were obtained in very good yields and enantiomeric excesses. Substituents at the C4–C7-positions of the quinolinium ring, irrespective to their electronic properties, were tolerated in the cycloaddition process, as well as several aryl substituents on the enamide moiety.…”

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.

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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.

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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.

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“…In 2022, Yoo's group explored the efficient methods for the synthesis of fused eight-membered N-heterocyclic compounds 119 (Scheme 25b). 52 In this transformation, quinolinium 1,4-zwitterions 24 were employed to react with enol diazoacetates 118 . Under the catalysis of CuCl, ligand L1 and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF), the reaction proceeded smoothly to give a wide range of chiral diazocine derivatives 119 in moderate to excellent yields with enantioselectivities.…”

Section: Cyclization Reactions Of Pyridinium 14-zwitterions and Pyrid...mentioning

confidence: 99%

Recent advances in the cyclization reactions of pyridinium 1,n-zwitterions (n = 4 and 5): scope and mechanism

2023

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“…Yoo et al also described a stereoselective (5 + 3) cyclization between quinolinium 1,4-zwitterions 2′ and enol diazoacetates 169 , catalyzed by Cu(I), as shown in Scheme 37 [ 109 ]. The desired diazocine derivatives ( S )- 173 could be synthesized in excellent yields (up to 97%) with perfect ee values (up to 97%) using a Cu(I)/bisoxazoline ligand L2 complex as a catalyst and a catalytic amount of NaBArF as an additive.…”

Section: Nitrogen-based Pyridinium and Quinolinium 14-zwitterionsmentioning

confidence: 99%

Recent Progress in Heterocycle Synthesis: Cyclization Reaction with Pyridinium and Quinolinium 1,4-Zwitterions

et al. 2023

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Heteroarene 1, n-zwitterions are powerful and versatile building blocks in the construction of heterocycles and have received increasing attention in recent years. In particular, pyridinium and quinolinium 1,4-zwitterions have been widely studied and used in a variety of cyclization reactions due to their air stability, ease of use, and high efficiency. Sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions, types of emerging heteroatom-containing synthons, have attracted much attention from chemists. These 1,4-zwitterions, which contain multiple reaction sites, have been successfully used in the synthesis of three- to eight-membered cyclic compounds over the last decade. In this review, we present the exciting progress made in the field of cyclization reactions of sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions. Moreover, the mechanistic insights, the transition states, some synthetic applications, and the challenges and opportunities are also discussed. We hope to provide an overview for synthetic chemists who are interested in the heterocycle synthesis from cyclization reaction with pyridinium and quinolinium 1,4-zwitterions pyridinium and quinolinium 1,4-zwitterions.

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Synthesis of Chiral Diazocine Derivatives via a Copper-Catalyzed Dearomative [5+3] Cycloaddition

Cited by 14 publications

References 30 publications

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

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

Recent advances in the cyclization reactions of pyridinium 1,n-zwitterions (n = 4 and 5): scope and mechanism

Recent Progress in Heterocycle Synthesis: Cyclization Reaction with Pyridinium and Quinolinium 1,4-Zwitterions

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