Lipase‐Catalyzed Dynamic Kinetic Resolution of C1‐ and C2‐Symmetric Racemic Axially Chiral 2,2′‐Dihydroxy‐1,1′‐biaryls

Moustafa, Gamal A. I.; Oki, Yasuhiro; Akai, Shuji

doi:10.1002/ange.201804161

Cited by 24 publications

(2 citation statements)

References 56 publications

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“…The most straightforward method for dynamic kinetic resolution of atropisomers consists of increas-ing the size of substituents to raise the barrier to rotation, such as electrophilic halogenation [11] and CÀ H activation. [12] A second approach involves alkylation [13] or acylation [14] of oxygen and nitrogen heteroatoms. A third alternative is based on ring manipulations by transition-metal catalysis, organocatalysis and enzyme catalysis.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Shi,

Fang,

Cheng

2024

Adv Synth Catal

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“…[16][17][18][19][20][21] Optically active atropisomers can be obtained via (dynamic) kinetic resolution in several cases that involve substrates bearing specific functional groups (Figure 1D). [22][23][24][25][26] Beyond these myriad of advances in transition-metal catalysis, recently organocatalyzed asymmetric synthesis of atropisomers has emerged as a powerful tool, and an array of interesting atropisomers with significant structural diversities were prepared. [27][28][29][30][31][32][33] Dynamic equilibrium of five-or six-membered-ring fused biaryls (A versus A 0 ) enables the facile asymmetric ring-opening reaction to access optically active atropisomers (Scheme 2A).…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Carbon-Carbon Bond Cleavage for Biaryl Atropisomers Synthesis

Deng

et al. 2019

Chem

112

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Development of new synthetic strategies for enantioselective carbon-carbon and carbon-heteroatom bond formation is one of the pillars of modern organic chemistry. Whereas significant advances have been achieved in center chirality construction, catalytically asymmetric construction of axial chirality is still under development. Moreover, axially chiral molecules constructed through carboncarbon and carbon-heteroatom bond cleavage are extremely limited. Here, we report an asymmetric synthesis of biaryl atropisomers via palladium-catalyzed chemoselective carbon-carbon cleavage of 9-aryl-9H-fluoren-9-ols. The reaction demonstrated broad substrate scope and produced the atropisomers in high yields and enantioselectivity. The ring-opening reactivity was considerably accelerated by the torsional strain created by the steric repulsion between two ortho-substituents of the biaryl skeleton in the substrates. The high enantiocontrol hinges on the evolvement of a new TADDOL-based phosphoramidite as ligand. These findings set up a new platform for the development of novel synthetic methods via asymmetric carbon-carbon cleavage.

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Advances in the Catalytic Asymmetric Synthesis of Atropisomeric Hexatomic N‐Heterobiaryls

Cheng

Shao

2020

Adv Synth Catal

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Axially chiral hexatomic N‐heterobiaryls are among the most important class of structures with extensive utility in asymmetric catalysis as chiral ligands and organocatalysts, as exemplified by QUINAP and QUINOX. Besides, these atropisomers have attracted broad attention due to their application in drug discovery. Hence, it is not surprising that extensive efforts have been devoted for the pursue of efficient catalytic asymmetric methods for their direct and atroposelective construction. In addition to the direct heteroaryl‐aryl cross‐coupling, which remains as a challenge, a series of creative catalytic asymmetric strategies based on pre‐formed heterobiaryl systems have been developed by taking advantage of the intrinsic property of N atom on the heteroarenes. Generally, the methods employed extensively involved kinetic resolution, dynamic kinetic asymmetric transformation, dynamic kinetic resolution and desymmetrization reaction. A growing number of approaches through stereoselective de novo formation of a six‐membered N‐heteroaromatic ring have also been reported for specific applications in this field. This review summarizes recent advancements of axially chiral hexatomic N‐heterobiaryls construction by means of asymmetric catalysis, including their scope, limitations, mechanisms and applications.magnified image

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Lipase‐Catalyzed Dynamic Kinetic Resolution of C₁‐ and C₂‐Symmetric Racemic Axially Chiral 2,2′‐Dihydroxy‐1,1′‐biaryls

Cited by 24 publications

References 56 publications

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Enantioselective Carbon-Carbon Bond Cleavage for Biaryl Atropisomers Synthesis

Advances in the Catalytic Asymmetric Synthesis of Atropisomeric Hexatomic N‐Heterobiaryls

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