Enantioselective Synthesis of 3,3′‐Disubstituted 2‐Amino‐2′‐hydroxy‐1,1′‐binaphthyls by Copper‐Catalyzed Aerobic Oxidative Cross‐Coupling

Zhao, Xiaojing; Li, Zi‐Hao; Ding, Tong‐Mei; Tian, Jin‐Miao; Tu, Yong‐Qiang; Wang, Aifang; Xie, Yuyang

doi:10.1002/ange.202015001

Cited by 17 publications

(6 citation statements)

References 70 publications

(26 reference statements)

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“…T he development of catalytic and enantioselective syntheses of axially chiral biaryls has been extensively explored [1][2][3][4][5][6][7] because it provides a highly efficient and selective route to access natural products 8,9 , biologically active compounds [10][11][12] , and chiral catalysts [13][14][15] . Strategies to control a stereogenic axis are generally classified into several categories [16][17][18][19][20][21][22][23] , such as direct cross-coupling, dynamic kinetic resolution, ring formation, and desymmetrization (Fig.…”

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confidence: 99%

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Kim

Lee

et al. 2023

Commun Chem

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Palladium-catalyzed asymmetric allylic alkylation has proven to be a powerful method for the preparation of a wide variety of chiral molecules. However, the catalytic and atroposelective allylic alkylation is still rare and challenging, especially for biaryl substrates. Herein, we report the palladium-catalyzed desymmetric and atroposelective allylation, in which the palladium complex with a chiral phosphoramidite ligand enables desymmetrization of nucleophilic 2-arylresorcinols in a highly enantioselective manner. With the aid of the secondary kinetic resolution effect, a wide variety of substrates containing a hydroxymethyl group at the bottom aromatic ring are able to provide O-allylated products up to 98:2 er. Computational studies show an accessible quadrant of the allylpalladium complex and provide three plausible transition states with intra- or intermolecular hydrogen bonding. The energetically favorable transition state is in good agreement with the observed enantioselectivity and suggests that the catalytic reaction would proceed with an intramolecular hydrogen bond.

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confidence: 99%

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Kim

Lee

et al. 2023

Commun Chem

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“…Subsequently, Ding [ 22 ] and Carreira [ 23 ] provided a series of improved approaches to enhance the synthetic efficiency and applicability in large-scale preparations and inhibit inseparable homo-coupling by-products. Recently, Tu and coworkers successfully constructed enantioenriched 3,3′-disubstituted NOBINs by aerobic oxidative cross-coupling utilizing a novel Cu/SPDO catalytic system [ 24 ]. The redox potential difference between two coupling partners ensured good chemoselectivity and chemical yield during the coupling process.…”

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confidence: 99%

Copper-Catalyzed Synthesis of Axially Chiral Biaryls with Diaryliodonium Salts as Arylation Reagents

Zhang

Xiang

et al. 2021

Molecules

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NOBIN and BINAM derivatives harboring biaryl frameworks are recognized as a class of important atropisomers with versatile applications. Here, we present an efficient synthetic route to access such compounds through copper-catalyzed domino arylation of N-arylhydroxylamines or N-arylhydrazines with diaryliodonium salts and [3,3]-sigmatropic rearrangement. This reaction features mild conditions, good substrate compatibility, and excellent efficiency. The practicality of this protocol was further extended by the synthesis of biaryl amino alcohols.

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“…These include reactions mediated by transition metals including copper 8-10 , iron 11 and vanadium, 12 amongst others. However, in the absence of specific functional groups, controlling the regio-, chemo-and enantioselectivity of the corresponding hetero-couplings remains a formidable challenge, and successful examples have been limited to the synthesis of BINOL or NOBIN type scaffolds [13][14][15][16] . In particular, Katsuki…”

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confidence: 99%

Enantioselective synthesis of atropisomeric indoles via iron-catalysed oxidative cross-coupling

et al. 2022

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Heterobiaryl compounds that exhibit axial chirality are of increasing value and interest across several fields, but direct oxidative methods for their enantioselective synthesis remain elusive. Here we disclose that an iron catalyst in the presence of a chiral PyBOX ligand and an oxidant enables direct coupling between naphthols and indoles to yield atropisomeric heterobiaryl compounds with high levels of enantioselectivity. The reaction exhibits remarkable chemoselectivity and exclusively yields cross-coupled products without competing homocoupling. Mechanistic investigations enable us to postulate that an indole radical is generated in the reaction but that this is likely an offcycle event, and that the reaction proceeds through formation of a chiral Fe-bound naphthoxy radical which is trapped by a nucleophilic indole. We envision that this simple, cheap, and sustainable catalytic manifold will facilitate access to a range of heterobiaryl compounds and enable their applications across the fields of materials science, medicinal chemistry, and catalysis.Atropisomeric biaryls comprise a privileged class of compounds whose applications span the fields of medicinal chemistry, catalysis and materials science; as such, a panoply of elegant and efficient methods have been developedfor their synthesis 1 . The most convergent route to biaryls is generally the transition metal mediated cross-coupling of two partners 2,3 (although significant advances in metal-free methods have been demonstrated recently) 4 . Whilst this strategy generally results in cross-coupled products in good yields and predictable levels of chemo-and regioselectivity, these advantages may be offset by the requirement to synthesize two specifically functionalized coupling partners (Figure 1a) 5 . In principle, oxidative coupling represents a more direct, atom economic and environmentally benign approach as it creates the desired aryl-aryl linkage from two C-H bonds 6,7 . This realization has led to a significant number of oxidative homo-coupling procedures that can generate C2-symmetric BINOL-like structures in an enantioselective fashion. These include reactions mediated by transition metals including copper 8-10 , iron 11 and vanadium, 12 amongst others. However, in the absence of specific functional groups, controlling the regio-, chemo-and enantioselectivity of the corresponding hetero-couplings remains a formidable challenge, and successful examples have been limited to the synthesis of BINOL or NOBIN type scaffolds [13][14][15][16] . In particular, Katsuki

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Enantioselective Synthesis of 3,3′‐Disubstituted 2‐Amino‐2′‐hydroxy‐1,1′‐binaphthyls by Copper‐Catalyzed Aerobic Oxidative Cross‐Coupling

Cited by 17 publications

References 70 publications

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Copper-Catalyzed Synthesis of Axially Chiral Biaryls with Diaryliodonium Salts as Arylation Reagents

Enantioselective synthesis of atropisomeric indoles via iron-catalysed oxidative cross-coupling

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