Enantioselective synthesis of cyclic α-aminoboronates <i>via</i> copper-catalyzed dearomative borylation of 4-quinolinols

Xu, Min; Ouyang, Yizhao; Wang, Linghua; Zhang, Shuai; Li, Pengfei

doi:10.1039/d2cc00027j

Cited by 3 publications

(4 citation statements)

References 62 publications

(16 reference statements)

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“…Very recently, Li and co-workers reported a regio- and enantioselective copper-catalyzed dearomative borylation of 4-quinolinols 21 , 37 obtained through N -selective Boc-protection of 4-hydroxiquinolines 20 ( Scheme 8 ). Treatment of a variety of N -Boc protected 4-quinolones 21 , with bis(pinacolato)diboron in the presence of CuCl as the catalyst, ( R , R )-Ph-BPE as a chiral ligand, t -BuONa as a base, and MeOH as the proton source, led to cyclic α-aminoboronates 22 in good yields with excellent enantioselectivities.…”

Section: Hydroboration Hydrosilylation and Reduction Reactionsmentioning

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: Hydroboration Hydrosilylation and Reduction Reactionsmentioning

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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“…65 As another example, Li et al reported the hydroboration of 4-quinolinols to give the corresponding bboryl compound without hydrolysis (Scheme 13d). 66 In addition to the commonly used copper catalysis, recent reports also involve some examples of cobalt catalysis. In 2022, Zhao et al reported a Co-catalyzed enantioselective hydroboration of silica-substituted alkenes.…”

Section: Borationmentioning

confidence: 99%

“…65 As another example, Li et al reported the hydroboration of 4-quinolinols to give the corresponding β-boryl compound without hydrolysis (Scheme 13d). 66…”

Section: Reactionsmentioning

confidence: 99%

Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Mei,

Ma,

Chen

et al. 2024

Chem. Soc. Rev.

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“…In recent years, copper-catalyzed conjugate addition reactions [ 32 ] of boron have emerged as a viable method to construct borylated heterocycles [ 33 , 34 ]. Among them, the dearomative borylation strategy of indoles [ 35 , 36 , 37 ], pyrroles [ 37 , 38 ], pyridines [ 39 ], and 4-quinolinols [ 40 ] have been efficiently utilized to construct borylated analogs of these biologically significant frameworks. Conjugate borylation of substituted esters and ketones has also been studied, which has demonstrated various challenges in the efficient conversion into corresponding borylated products [ 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

Development of a New Methodology for Dearomative Borylation of Coumarins and Chromenes and Its Applications to Synthesize Boron-Containing Retinoids

et al. 2023

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Dearomative borylation of coumarins and chromenes via conjugate addition represents a relatively unexplored and challenging task. To address this issue, herein, we report a new and general copper (I) catalyzed dearomative borylation process to synthesize boron-containing oxacycles. In this report, the borylation of coumarins, chromones, and chromenes comprising functional groups, such as esters, nitriles, carbonyls, and amides, has been achieved. In addition, the method generates different classes of potential boron-based retinoids, including the ones with oxadiazole and anthocyanin motifs. The borylated oxacycles can serve as suitable intermediates to generate a library of compounds.

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Enantioselective synthesis of cyclic α-aminoboronates via copper-catalyzed dearomative borylation of 4-quinolinols

Abstract: A highly enantioselective and regioselective dearomative borylation of 4-quinolinols was developed using Cu(I)/(R,R)-Ph-BPE catalyst for efficient synthesis of unprecedented heterocyclic α-amino boronates, a new class of compounds potentially relevant to...

Cited by 3 publications

References 62 publications

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

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

Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Development of a New Methodology for Dearomative Borylation of Coumarins and Chromenes and Its Applications to Synthesize Boron-Containing Retinoids

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