Biocatalytic Dynamic Kinetic Resolution for the Synthesis of Atropisomeric Biaryl N‐Oxide Lewis Base Catalysts

Staniland, Samantha; Adams, Ralph W.; McDouall, Joseph J. W.; Maffucci, Irene; Contini, Alessandro; Grainger, Damian M.; Turner, Nicholas J.; Clayden, Jonathan

doi:10.1002/ange.201605486

Cited by 35 publications

(4 citation statements)

References 63 publications

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“…The preparation of axially chiral QUINOL scaffolds via kinetic resolution is pioneered by You and Gu in 2014, where Pd(II)-catalyzed direct C–H iodination forged axially chiral isoquinoline N-oxides with moderate enantioselectivity 31 . A biocatalytic dynamic kinetic resolution enabled by configurational lability of precursors was then prominently disclosed by Clayden and Turner 32 . Diversely, Matsubara and Asano attained a highly enantioselective aromatic electrophilic bromination of 1-(3-hydroxyphenyl)isoquinoline 2-oxides to construct axially chiral isoquinoline N-oxides by using a bifunctional catalyst 33 .…”

Section: Resultsmentioning

confidence: 99%

Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives

Jiang

Fan

et al. 2021

Nat Commun

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As an important platform molecule, atropisomeric QUINOL plays a crucial role in the development of chiral ligands and catalysts in asymmetric catalysis. However, efficient approaches towards QUINOL remain scarce, and the resulting high production costs greatly impede the related academic research as well as downstream industrial applications. Here we report a direct oxidative cross-coupling reaction between isoquinolines and 2-naphthols, providing a straightforward and scalable route to acquire the privileged QUINOL scaffolds in a metal-free manner. Moreover, a NHC-catalyzed kinetic resolution of QUINOL N-oxides with high selectivity factor is established to access two types of promising axially chiral Lewis base catalysts in optically pure forms. The utility of this methodology is further illustrated by facile transformations of the products into QUINAP, an iconic ligand in asymmetric catalysis.

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Section: Resultsmentioning

confidence: 99%

Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives

Jiang

Fan

et al. 2021

Nat Commun

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“…Accordingly, they developed a biocatalytic DKR approach to produce axially chiral biarylpyridines and isoquinoline N-oxides by performing aldehyde reduction (Scheme 23a). [53] Last year, Wang's group reported organocatalyzed DKR of such configurationally unstable heterobiaryl aldehydes (Scheme 23b). [54] The process is fulfilled through a cascade condensation/ cyclization of aminobenzamides 59 with the formyl group in 57 in the presence of CPA Cat.…”

Section: Dkr Via Transient Ring Formation By Intramolecular Hydrogen ...mentioning

confidence: 99%

“…The presence of a strong bonding interaction between the oxygen of the N‐oxide and the carbon of the aldehyde at the six‐membered ring transition state TS‐3 in biaryl N‐oxide 57 a (ΔG ≠ =16.3 kcal/mol) was revealed by Clayden, Turner and co‐workers in 2016. Accordingly, they developed a biocatalytic DKR approach to produce axially chiral biarylpyridines and isoquinoline N‐oxides by performing aldehyde reduction (Scheme 23a) [53] . Last year, Wang's group reported organocatalyzed DKR of such configurationally unstable heterobiaryl aldehydes (Scheme 23b) [54] .…”

Section: Dkr Via Transient Ring Formation By Intramolecular Hydrogen ...mentioning

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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“…Fortunately, organocatalytic asymmetric cross‐coupling or arylation has achieved the construction of heterobiaryls, as reported by Shi, [8a] Tan, [8b,d] Miller ,[8c] and other groups. Additionally, functionalization of racemic heterobiaryls via dynamic kinetic resolution [7a–c] is mainly reported by Miller, [9a,j] You, [9b–d] Li, [9e] Lassaletta, [9f,g] Stoltz and Virgil, [9h] Turner and Clayden [9i] neatly illustrate the great potential of this method in building heterobiaryl skeletons. On the other hand, cycloaddition and cyclization reactions are one of the most powerful synthetic methods for the rapid construction of cyclic frameworks, owing to their high atom economy and convergent nature [10] .…”

Section: Introductionmentioning

confidence: 96%

Atroposelective Synthesis of Heterobiaryls through Ring Formation

Sun

Sharif

Chen

et al. 2023

Chemistry A European J

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Atropisomeric heterobiaryls play a vital role in natural products, chiral ligands, organocatalysts, and other research fields, which have aroused great interest from chemists in recent years. Until now, a growing number of optically active heterobiaryls based on indole, quinoline, isoquinoline, pyridine, pyrrole, azole, and benzofuran skeletons have been successfully synthesized through metal or organic catalytic cross-coupling, functionalization of prochiral or racemic heterobiaryls, and ring formation. Among different strategies for the atroposelective synthesis of heterobiaryls, the strategy of ring formation has become a vital tool toward this goal. In this review, we summarize the enantioselective synthesis of axially chiral heterobiaryls through ring formation approaches, such as cycloaddition, cyclization, and chirality conversion. Meanwhile, the reaction mechanism and the corresponding applications of the chiral heterobiaryls are also discussed.[a] H.

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Biocatalytic Dynamic Kinetic Resolution for the Synthesis of Atropisomeric Biaryl N‐Oxide Lewis Base Catalysts

Cited by 35 publications

References 63 publications

Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives

Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Atroposelective Synthesis of Heterobiaryls through Ring Formation

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