Remote control over both site-selectivity and atroposelectivity of Suzuki–Miyaura coupling through distal ionic interactions

On, Ivan Keng Wee; Hong, Wenyang; Zhu, Ye

doi:10.1016/j.tetlet.2023.154408

Cited by 3 publications

(3 citation statements)

References 27 publications

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“…This account summarizes our recent work on developing chiral dialkyl biarylphosphine ligands that possess nonligating ionic groups in order to exert long-range stereocontrol in Suzuki-Miyaura reactions. [15][16][17][18]…”

Section: Account Synlettmentioning

confidence: 99%

“…Furthermore, we have utilized ionic catalyst-substrate interactions to serve a dual role in a reaction, i.e., mediating both stereoselectivity and site-selectivity (Scheme 8). 18 Using 3,4-dichloroarenes bearing 1-ionizable groups, functionalized biaryl chlorides can be prepared readily with good atropo-enantioselectivity and with modest site-selectivity for coupling at the 3-position. The results illustrate the versatility of ionic-interactions-directed selectivity control, especially when the two types of selectivity are likely set at different elementary steps of the catalytic cycle.…”

Section: Cluster Account Synlettmentioning

confidence: 99%

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Enantioselective Palladium-Catalyzed Suzuki–Miyaura Reactions Enabled by Ionic Ligand–Substrate Interactions

Zhu

2023

Synlett

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Enzymes harness an array of noncovalent interactions to accomplish stereospecific transformations. Similarly, chemists have engineered chiral catalysts capable of eliciting noncovalent interactions for asymmetric synthesis. In this context, incorporating ionic groups into synthetic transition-metal catalysts represents a promising design element for enantioselective reactions by engaging electrostatic interactions between ligands and substrates. However, the nondirectional nature of ionic interactions presents a unique challenge in precise transmission of chirality. This account seeks to summarize our recent work on developing phosphine ligands possessing nonligating ionic groups to exert long-range stereocontrol in Suzuki–Miyaura reactions.

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Section: Account Synlettmentioning

confidence: 99%

Section: Cluster Account Synlettmentioning

confidence: 99%

Enantioselective Palladium-Catalyzed Suzuki–Miyaura Reactions Enabled by Ionic Ligand–Substrate Interactions

Zhu

2023

Synlett

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“…34 Following the three-step synthesis we initially devised, both enantiomers of L5 are accessible in enantioenriched forms. Subsequently, bromination of (S a )-L5 followed by carboxylation 35 using CO 2 yielded axially chiral 3′-carboxyl ligand L6.…”

Section: ■ Introductionmentioning

confidence: 99%

Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters

2023

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Synthetic application of asymmetric catalysis relies on strategic alignment of bond construction to creation of chirality of a target molecule. Remote desymmetrization offers distinctive advantages of spatial decoupling of catalytic transformation and generation of a stereogenic element. However, such spatial separation presents substantial difficulties for the chiral catalyst to discriminate distant enantiotopic sites through a reaction three or more bonds away from a prochirality center. Here, we report a strategy that establishes acyclic quaternary carbon stereocenters through cross-coupling reactions at distal positions of aryl substituents. The new class of amino acid-derived ionic chiral catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki–Miyaura reaction, Sonogashira reaction, and Buchwald–Hartwig amination between diverse diarylmethane scaffolds and aryl, alkynyl, and amino coupling partners, providing rapid access to enantioenriched molecules that project substituents to widely spaced positions in the three-dimensional space. Experimental and computational investigations reveal electrostatic steering of substrates by the C-terminus of chiral ligands through ionic interactions. Cooperative ion-dipole interactions between the catalyst’s amide group and potassium cation aid in the preorganization that transmits asymmetry to the product. This study demonstrates that it is practical to achieve precise long-range stereocontrol through engineering the spatial arrangements of the ionic catalysts’ substrate-recognizing groups and metal centers.

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Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling

Li,

Ho,

et al. 2024

Chem

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Remote control over both site-selectivity and atroposelectivity of Suzuki–Miyaura coupling through distal ionic interactions

Cited by 3 publications

References 27 publications

Enantioselective Palladium-Catalyzed Suzuki–Miyaura Reactions Enabled by Ionic Ligand–Substrate Interactions

Enantioselective Palladium-Catalyzed Suzuki–Miyaura Reactions Enabled by Ionic Ligand–Substrate Interactions

Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters

Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling

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