Enantioselective Synthesis of Atropisomeric Biaryls by Pd‐Catalyzed Asymmetric Buchwald–Hartwig Amination

Zhang, Peng; Wang, Xiaomei; Xu, Qi; Guo, Chang‐Qiu; Wang, Peng; Lu, Chuan‐Jun; Liu, Renrong

doi:10.1002/ange.202108747

Cited by 18 publications

(3 citation statements)

References 62 publications

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“…[147][148] Recently, various research groups have conducted extensive studies on the formation of CÀ N bond, using palladium catalysis. [149][150] Hitherto, vicinal diamination of alkenes and alkyne analogue scarcely explored. To explore this, Jieping Zhu and co-workers disclosed domino intramolecular oxidative-palladium catalyzed reactions of 1,2-diarylethynes as hitherto underdeveloped substrates for vicinal diamination, to provide chemoselective and inevitable access to tetracyclic N-[2-(methoxycarbonyl)ethyl]indoloiso quinolineones in good to excellent yields (Scheme 17).…”

Section: Pd(ii)-catalyzed 12-diaminationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Kumar

2023

Chemistry An Asian Journal

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1,2‐Diamines are synthetically important motifs in organo‐catalysis, natural products, and drug research. Continuous utilization of transition‐metal based catalyst in direct 1,2‐diamination of olefines, in contrast to metal‐free transformations, with numerous impressive advances made in recent years (2015‐2023). This review summarized contemporary research on the transition‐metal catalyzed/mediated [e.g., Cu(II), Pd(II), Fe(II), Rh(III), Ir(III), and Co(II)] 1,2‐diamination (asymmetric and non‐asymmetric) especially emphasizing the recent synthetic methodologies and mechanistic understandings. Moreover, up‐to‐date discussion on (i) paramount role of oxidant and catalyst (ii) key achievements (iii) generality and uniqueness, (iv) synthetic limitations or future challenges, and (v) future opportunities are summarized related to this potential area.

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Section: Pd(ii)-catalyzed 12-diaminationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Kumar

2023

Chemistry An Asian Journal

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“…However, synthetic examples are limited. 37,40,46,47 Indeed, C-H bond activation has been established as an increasingly important strategy in asymmetric synthesis of axially chiral biaryls, [48][49][50] including de novo construction of rings in C-N axially chiral biaryls (Scheme 1b). Recently, Zhou realized synthesis of isoqionolones via palladium-catalyzed Catellani reactions using bifunational and bulky aryl bromides.…”

Section: Chiral Ligands Have Also Been Demonstratedmentioning

confidence: 99%

Enantioselective Access to C-N Axially Chiral Isoquinolones via Dynamic Kinetic Transformation of Carbene Reagents: Unique Chiral Induction Enabled by Dual Role of the Catalyst

Wang

Zhang

et al. 2022

Preprint

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Isoquinolones are important structural motifs in synthetic and medicinal chemistry. Reported herein is highly atroposelective access to C-N axially chiral isoqionolones via rhodium-catalyzed C-H activation of N-alkoxy benzamides and [3+3] annulation with imidoyl sulfoxonium ylides. The coupling system proceeded efficiently under mild and redox-neutral conditions with excellent functional group tolerance as a result of dynamic kinetic transformation of the ylidic coupling reagent (carbene precursor). Experimental and computational studies revealed a pathway of C-H activation, carbene insertion, and formal nucleophilic substitution-cyclization for this coupling system. In particular, the C-N cyclization is enantio-determining and occurs via an unusual rhodium-catalyzed -bond metathesis mechanism. The benzamide, the imidoyl sulfoxonium ylide, and the chiral catalyst each played a dual role. The amide functionality acts as a directing group as well as an electrophilic acylating group, and the imidoyl sulfoxonium ylide participated as a nucleophile-functionalized carbene reagent. Applications of representative products as potentially useful chiral ligands have also been demonstrated.

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“…[1][2][3][4][5][6] Several powerful strategies have been established, such as metal-or organocatalyzed enantioselective CÀ N coupling, [7][8][9][10][11] de novo synthesis of arenes or heteroarenes, [12][13][14][15][16][17][18][19][20] desymmetrization process [21][22][23][24][25][26] and dynamic kinetic resolution (DKR). [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] However, there still remains a pressing need to develop new approaches to enhance the diversity of CÀ N atropisomers, especially the biologically active motifs. Isoquinoline-1,3 (2H,4H)-diones are such a kind of pharmaceutical and bioactive molecules (Figure 1).…”

mentioning

confidence: 99%

Regio‐ and Atroposelective Ring‐Opening of 1H‐Benzo[4,5]oxazolopyridinones

Deng,

Dong,

et al. 2024

Angewandte Chemie

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The development of new methods for regio‐ and stereoselective activation of C‐O bonds in ethers holds significant promise for synthetic chemistry, offering advantages in terms of environmental sustainability and economic efficiency. Moreover, the C–N atropisomers represent a fascinating and crucial chiral system, extensively found in natural products, pharmaceutical leads, and the frameworks of advanced materials. In this work, we have introduced a nickel‐catalyzed regio‐ and enantioselective carbon‐oxygen arylation reaction for atroposelective synthesis of N‐arylisoquinoline‐1,3(2H,4H)‐diones. The high regioselectivity of C–O cleavage benefits from the high stability of the in‐situ formed (amido)ethenolate via oxidative addition. Additionally, the self‐activation of the aryl C–O bond facilitates the reaction under mild conditions, leading to outstanding enantioselectivities. The diverse post‐functionalizations of the axially chiral isoquinoline‐1,3(2H,4H)‐diones further highlighted the utility of this protocol in preparing valuable C–N atropisomers, including the chiral phosphine ligands.

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Enantioselective Synthesis of Atropisomeric Biaryls by Pd‐Catalyzed Asymmetric Buchwald–Hartwig Amination

Cited by 18 publications

References 62 publications

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Enantioselective Access to C-N Axially Chiral Isoquinolones via Dynamic Kinetic Transformation of Carbene Reagents: Unique Chiral Induction Enabled by Dual Role of the Catalyst

Regio‐ and Atroposelective Ring‐Opening of 1H‐Benzo[4,5]oxazolopyridinones

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