Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc‐Catalyzed Asymmetric Hydrosilylation

Hornillos, Valentı́n; Carmona, José Ariza; Ros, Abel; Iglesias‐Sigüenza, Javier; López‐Serrano, Joaquín; Fernández, Rosario; Lassaletta, José M.

doi:10.1002/ange.201713200

Cited by 28 publications

(2 citation statements)

References 63 publications

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“…Similar Lewis acid-base interactions (LABI) have also been reported to be present in the compounds depicted in Figure 2 letta, Fernandez, Hornillos and co-workers documented a Zn-catalyzed asymmetric hydrosilylation of heterobiaryl ketones 64 of which the Lewis pair formed between nitrogen atom and the carbonyl group is responsible for the labilization of the stereogenic axis (Figure 2a). [55] The same group further expanded such LABI-enable DKR methodologies recently, including biocatalytic reduction of N-arylindole aldehydes 65 relying on the formation a transient six-membered transition state (Figure 2b), [56] iridium-catalyzed transfer hydrogenative allylation of 2-(quinolin-8yl)benzaldehydes 66 through LABI between the quinoline nitrogen atom and the aldehyde carbonyl group (Figure 2c) [57] and rhodium-catalyzed reductive aldol reaction of ortho'-sulfenyl 3-aryl indole 2carbaldehydes 67 by means of an attractive SR•••CHO LABI in the 6-membered cyclic transition state (Figure 2d). [58]…”

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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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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“…[11][12][13] There is only one example of constructing five-five-membered furan-based scaffolds, which was reported by Zhu's group using the central-to-axial chirality conversion strategy under asymmetric metalcatalysis. [14] In recent years, the catalytic asymmetric synthesis of molecules bearing both axial and central chirality has become an emerging area [15][16] because the introduction of central chirality to atropisomers provides an opportunity to incorporate new properties into axially chiral molecules. Nevertheless, catalytic asymmetric construction of furanbased scaffolds bearing both axial and central chirality was almost undisclosed except that Zhao's group reported the construction of axially chiral 3-arylbenzofurans bearing another stereogenic center via an organocatalytic asymmetric cascade reaction.…”

Section: Introductionmentioning

confidence: 99%

Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

Wang,

Gao,

et al. 2024

Angew Chem Int Ed

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In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing to the importance and difficulty in constructing such frameworks. In this work, we have realized the first catalytic asymmetric synthesis of five‐five‐membered furan‐based compounds bearing both axial and central chirality via organocatalytic asymmetric (2+4) annulation of achiral furan‐indoles with 2,3‐indolyldimethanols with uncommon regioselectivity. By this strategy, furan‐indole compounds bearing both axial and central chirality were synthesized in high yields with excellent regio‐, diastereo‐, and enantioselectivities. Moreover, theoretical calculations were conducted to provide an in‐depth understanding of the reaction pathway, activation mode, and the origin of the selectivity.

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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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Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc‐Catalyzed Asymmetric Hydrosilylation

Cited by 28 publications

References 63 publications

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations

Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

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

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