Cooperative catalysis-enabled C–N bond cleavage of biaryl lactams with activated isocyanides

Wang, Wen-Tao; Zhang, Sen; Tao, Ling-Fei; Pan, Ziqi; Qian, Linghui; Liao, Jia‐Yu

doi:10.1039/d2cc01625g

Cited by 18 publications

(5 citation statements)

References 46 publications

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“…This DKR approach afforded a new family of enantioenriched axially chiral oxazole‐substituted biaryl phenols in high yields employing Ag 2 CO 3 as metal salt and quinidine‐derived phosphine as chiral ligand [31] . Along the same line, the authors then extended this strategy to the ring opening of biaryl lactams [32] and thionolactones [20] …”

Section: Dkr Via Ring Opening Of Biaryl Lactones/lactamsmentioning

confidence: 99%

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Shi,

Fang,

Cheng

2024

Adv Synth Catal

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Axially chiral architectures exist widely in natural products, biologically relevant molecules, chiral ligands and catalysts as well as functional materials. Therefore, catalytic asymmetric synthesis of atropisomers has become one of the most fast‐growing fields in the community of chemistry and rapid advances have occurred. Among different methods reported, the organocatalytic atroposelective dynamic kinetic resolution (DKR) involving ring manipulations stands out as a cutting‐edge technology to construct axial chirality from the point of atom/step economy. In this DKR strategy, the configurational lability of starting materials originates from chirally‐labile ring structure of cyclic substrates/intermediates or transient ring formation through noncovalent interactions from acyclic substrates. The two atropisomers of starting material are in equilibrium in the reaction medium, ensuring the constant transformation of the less reactive atropisomer into the more reactive one, and then to a single enantiopure product in the presence of an appropriate organocatalyst. This review summarizes recent advancements on this topic, including their scopes, limitations, mechanisms, applications and provides some insights into further developments. 1. Introduction 2. DKR via Ring Opening of Biaryl Lactones/Lactams 3. DKR via Ring Opening of Cyclic Intermediates 4. DKR via Transient Ring Formation by Intramolecular Hydrogen Bonding or Lewis Acid‐Base Interaction 5. Conclusions and Outlook 6. References

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Section: Dkr Via Ring Opening Of Biaryl Lactones/lactamsmentioning

confidence: 99%

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Shi,

Fang,

Cheng

2024

Adv Synth Catal

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“…Catalytic asymmetric ring‐opening of dibenzo fused five‐ or six‐membered compounds has emerged as a successful strategy for the synthesis of C−C atropisomers [46] . Previous researches have successfully established the asymmetric ring‐opening of biaryl lactones or lactams by Bringmann, Wang, Zhang, Fu, et al [47–53] . Our group realized atroposelective synthesis of biaryls through the ring‐opening of cyclic diaryliodoniums, [54–57] 9‐fluorenols, [58] silafluorenes, [59] and dibenzothiopheniums [60] .…”

Section: Figurementioning

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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“…In 2022, the Liao group extended this nucleophilic isocyanide ring opening strategy to the ring opening of biaryl lactams (Figure 60). 233 Given the relatively low electrophilicity of lactams as compared to their lactone counterparts, the authors envisioned that using a squaramide catalyst could sufficiently activate the carbonyl for nucleophilic attack through hydrogen bonding. With 60.1 and isocyanoacetamide 60.2 as model substrates, they identified a catalytic diad of Ag 2 CO 3 and quinidine-derived squaramide organocatalyst 60.3, which led to the formation of oxazole 60.4 in 98% yield and 98% ee.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

Roos,

Chiang,

Murray

et al. 2023

Chem. Rev.

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Cooperative catalysis-enabled C–N bond cleavage of biaryl lactams with activated isocyanides

Abstract: The catalytic reaction of biaryl lactams with activated isocyanides is reported for the first time. By employing a cooperative catalytic system, oxazole-containing axially chiral biaryl anilines were obtained in high...

Cited by 18 publications

References 46 publications

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

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

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

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