Alkali-metal bases in catalytic hydrogen isotope exchange processes

Tortajada, Andreu; Hevia, Eva

doi:10.1039/d3cy00825h

Cited by 10 publications

(1 citation statement)

References 48 publications

(47 reference statements)

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“…Moreover, the harsh conditions, stoichiometric amounts of strong bases, and limited substrate scope of the DoM approach significantly restrict its application in tritium labeling. The catalytic HIE of benzylic and aromatic C–H bonds was recently reported with alkali and alkaline earth amide catalysts . We recently reported the HIE of benzylic C–H bonds with cesium amide as a catalyst through a kinetic deprotonative equilibrium .…”

Section: Introductionmentioning

confidence: 87%

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Du,

Li,

Christodoulou

et al. 2024

ACS Catal.

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Section: Introductionmentioning

confidence: 87%

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Du,

Li,

Christodoulou

et al. 2024

ACS Catal.

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Masters of Mediation: MN(SiMe₃)₂ in Functionalization of C(sp³)−H Latent Nucleophiles

Sreedharan,

Gandhi

2024

Chemistry A European J

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Organoalkali compounds have undergone a far‐reaching transformation being a coupling partner to a mediator in unusual organic conversions which finds its spot in the field of sustainable synthesis. Transition‐metal catalysis has always been the priority in C(sp3)−H bond functionalization, however alternatively, in recent times this has been seriously challenged by earth‐abundant alkali metals and their complexes arriving at new sustainable organometallic reagents. In this line, the importance of MN(SiMe3)2 (M = Li, Na, K & Cs) reagent revived in C(sp3)−H bond functionalization over recent years in organic synthesis is showcased in this minireview. MN(SiMe3)2 reagent with higher reactivity, enhanced stability, and bespoke cation‐π interaction have shown eye‐opening mediated processes such as C(sp3)−C(sp3) cross‐coupling, radical‐radical cross‐coupling, aminobenzylation, annulation, aroylation, and other transformations to utilize readily available petrochemical feedstocks. This article also emphasizes the unusual reactivity of MN(SiMe3)2 reagent in unreactive and robust C−X (X = O, N, F, C) bond cleavage reactions that occurred alongside the C(sp3)−H bond functionalization. Overall, this review encourages the community to exploit the untapped potential of MN(SiMe3)2 reagent and also inspires them to take up this subject to even greater heights.

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Deuterated Alkyl Sulfonium Salt Reagents; Importance of H/D Exchange Methods in Drug Discovery

Ogasahara,

Ban,

Mae

et al. 2024

ChemMedChem

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Deuterated drugs (heavy drugs) have recently been spotlighted as a new modality for small‐molecule drugs because the pharmacokinetics of pharmaceutical drugs can be enhanced by replacing C‐H bonds with more stable C‐D bonds at metabolic positions. Therefore, deuteration methods for drug candidates are a hot topic in medicinal chemistry. Among them, the H/D exchange reaction (direct transformation of C‐H bonds to C‐D bonds) is a useful and straightforward method for creating novel deuterated target molecules, and over 20 reviews on the synthetic methods related to H/D exchange reactions have been published in recent years. Although various deuterated drug candidates undergo clinical trials, approved deuterated drugs possess CD3 groups in the same molecule. However, less diversification, except for the CD3 group, is a problem for future medicinal chemistry. Recently, we developed various deuterated alkyl (dn‐alkyl) sulfonium salts based on the H/D exchange reaction of the corresponding hydrogen form using D2O as an inexpensive deuterium source to introduce CD3, CH3CD2, and ArCH2CD2 groups into drug candidates. This concept summarises recent reviews related to H/D exchange reactions and novel reagents that introduce the CD3 group, and our newly developed electrophilic dn‐alkyl reagents are discussed.

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Alkali-metal bases in catalytic hydrogen isotope exchange processes

Abstract: The preparation of compounds labeled with deuterium or tritium has become an essential tool in different research fields. Hydrogen isotope exchange (HIE) offers a direct access to said compounds, introducing...

Cited by 10 publications

References 48 publications

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Masters of Mediation: MN(SiMe₃)₂ in Functionalization of C(sp³)−H Latent Nucleophiles

Deuterated Alkyl Sulfonium Salt Reagents; Importance of H/D Exchange Methods in Drug Discovery

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Alkali-metal bases in catalytic hydrogen isotope exchange processes

Abstract: The preparation of compounds labeled with deuterium or tritium has become an essential tool in different research fields. Hydrogen isotope exchange (HIE) offers a direct access to said compounds, introducing...

Cited by 10 publications

References 48 publications

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Directed Aromatic Deuteration and Tritiation of Pharmaceuticals by Heavy Alkali Metal Amide Catalysts

Masters of Mediation: MN(SiMe3)2 in Functionalization of C(sp3)−H Latent Nucleophiles

Deuterated Alkyl Sulfonium Salt Reagents; Importance of H/D Exchange Methods in Drug Discovery

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Product

Resources

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Masters of Mediation: MN(SiMe₃)₂ in Functionalization of C(sp³)−H Latent Nucleophiles