Synthesis of axially chiral diaryl ethers <i>via</i> NHC-catalyzed atroposelective esterification

Wu, Yingtao; Guan, Xin; Zhao, Huaqiu; Li, Mingrui; Liang, Tianlong; Sun, Jiaqiong; Zheng, Guangfan; Zhang, Qian

doi:10.1039/d3sc06444a

Cited by 12 publications

(1 citation statement)

References 85 publications

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“…SO 2 could undergo reversible coupling 30 with propargyl or allene radicals, serving as a hidden radical concentration buffer to promote the radical monofluoromethylative acylation of 1,3-enynes. As a result of our continuous interest in NHC catalysis, 28 b ,29 a ,31 we now report our discovery in NHC and photocatalysis dual-catalyzed SO 2 -participating three-component radical monofluoromethylative acylation of 1,3-enynes, providing direct access to monofluoromethyl-substituted tetrasubstituted allenyl ketones (Scheme 1C). Furthermore, this strategy could be extended to the radical difluoromethylative acylation of 1,3-enynes.…”

Section: Introductionmentioning

confidence: 99%

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes

Xia,

Ma,

Wang

et al. 2024

Org. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes

Xia,

Ma,

Wang

et al. 2024

Org. Chem. Front.

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Catalytic Enantioselective Synthesis of Axially Chiral Diaryl Ethers Via Asymmetric Povarov Reaction Enabled Desymmetrization

Ye,

Xie,

Liu

et al. 2024

Advanced Science

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Axially chiral diaryl ethers represent a distinct class of atropisomers, characterized by a unique dual C─O axes system, which have been found in a variety of natural products, pharmaceuticals, and ligands. However, the catalytic enantioselective synthesis of these atropoisomers poses significant challenges, due to the difficulty in controlling both chiral C─O axes, and their more flexible conformations. Herein, an efficient protocol for catalytic enantioselective synthesis of axially chiral diaryl ethers is presented using organocatalyzed asymmetric Povarov reaction‐enabled desymmetrization, followed by aromatizations. This method yields a wide range of novel quinoline‐based diaryl ether atropoisomers in good yields and high enantioselectivities. Notably, various aromatization protocols are developed, resulting in a diverse set of polysubstituted quinoline‐containing diaryl ether atropisomers. Thermal racemization studies suggested excellent configurational stabilities for these novel diaryl ether atropisomers (with racemization barriers up to 38.1 kcal mol−1). Moreover, this research demonstrates for the first time that diaryl ether atropisomers lacking the bulky t‐Bu group can still maintain a stable configuration, challenging the prior knowledge in the field. The fruitful derivatizations of the functional group‐rich chiral products further underscore the value of this method.

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Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers

Naghim,

Rodriguez,

Chuzel

et al. 2024

Angewandte Chemie

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Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also for their biological importance and wide‐ranging applications as chiral materials, ligands, and organocatalysts. While biaryl and heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom‐linked non‐biaryl atropisomers presents a formidable challenge in modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting in low barriers to enantiomerization through concerted bond rotations. In recent years the discovery of new configurationally stable rare non‐biaryl scaffolds such as aryl amines, aryl ethers and aryl sulfones as well as innovative methodologies to control their configuration have been disclosed in the literature and constitute the topic of this minireview.

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Synthesis of axially chiral diaryl ethers via NHC-catalyzed atroposelective esterification

Abstract: We present NHC-catalyzed atroposelective esterification of prochiral dialdehydes, delivering enantioenriched axially chiral diaryl ethers. Matched kinetic resolutions amplify the enantioselectivity by removing minor enantiomers via over-functionalization.

Cited by 12 publications

References 85 publications

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes

Catalytic Enantioselective Synthesis of Axially Chiral Diaryl Ethers Via Asymmetric Povarov Reaction Enabled Desymmetrization

Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers

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