Facile and general electrochemical deuteration of unactivated alkyl halides

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Июнь 30, 2022

Abstract Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides OMs) using D 2 O as the economical deuterium source was reported. In addition to primary secondary halides, sterically hindered tertiary chlorides also work very well, affording target deuterodehalogenated products with excellent efficiency incorporation. More than 60 examples are provided, including late-stage dehalogenative natural products, pharmaceuticals, their derivatives, all incorporation (up 99% D), demonstrating potential utility developed method in organic synthesis. Furthermore, does not require external catalysts tolerates high current, showing possible use industrial applications.

Язык: Английский

---

Interfacing single-atom catalysis with continuous-flow organic electrosynthesis

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 3898 - 3925

Опубликована: Янв. 1, 2022

This manuscript reviews for the first time developments at interface between organic electrosynthesis and single-atom catalysis, highlighting advantages in shifting from a batch to flow production.

Язык: Английский

---

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Язык: Английский

---

Electroreduction of unactivated alkenes using water as hydrogen source

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 30, 2024

Abstract Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination anodic iron salts and silane generated in situ via cathodic reduction, using H 2 O as H-source. The catalytic amounts Si-additive work H-carrier from to generate a highly active species under continuous electrochemical conditions. This approach shows broad substrate scope good functional group compatibility. In addition hydrogenation, use D instead provides desired deuterated products yields with excellent D-incorporation (up >99%). Further late-stage hydrogenation complex molecules drug derivatives demonstrate potential application pharmaceutical industry. Mechanistic studies are performed provide support for proposed mechanistic pathway.

Язык: Английский

---

Deuterodehalogenation Under Net Reductive or Redox‐Neutral Conditions Enabled by Paired Electrolysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 4, 2023

Interest in deuterated active pharmaceutical ingredients (APIs) is increasing as deuteration holds promise for kinetic isotope effect (KIE) regulated fine-tuning of API performance. Moreover, deuterium labeling frequently carried out to study organic and bioorganic reaction mechanisms facilitate complex target synthesis. As such, methods highly selective molecules are desirable. Herein, we present an electrochemical method the deuterodehalogenation benzylic halides via a radical-polar crossover mechanism, using inexpensive oxide (D

Язык: Английский

---

Recent Advances in Deuteration Reactions^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 42(10), С. 1145 - 1156

Опубликована: Дек. 26, 2023

Comprehensive Summary The deuteration of organic compounds has attracted more attentions in recent years for the potential applications new drug discovery and synthetic chemistry. For this purpose, many efficient deuterium labeling methodologies have been developed, including hydrogen isotope exchange (HIE), reductive deuteration, dehalogenative that allow synthesis selectively deuterated compounds. In last few years, great breakthroughs selective achieved interest molecules is rising. review, we summarized developments since 2021. Several types key processes incorporation reactions, H/D exchange, are introduced discussed. Key Scientists 2000s, Derdau Atzrodt's group made contributions to directing assisted noble‐metal catalyzed arenes labeled During same period, Sajiki co‐workers completed a series reactions by heterogeneous platinum‐group metal catalysts. Since 2015, Gregory Pieters developed ruthenium catalysts exchange. 2016, Chirik's presence homogeneous iron complex. David MacMillan coworkers photocatalyzed HIE α‐amino C(sp 3 )–H bonds. From 2020, nanoelectrodes were designed deuterations unactivated unsaturated bonds Zhang's group. Recently, Beller's several strategies isotopic using earth‐abundant Our review latest important

Язык: Английский

---

eHydrogenation: Hydrogen‐free Electrochemical Hydrogenation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Авг. 4, 2023

Hydrogenation reactions are staple transformations commonly used across scientific fields to synthesise pharmaceuticals, natural products, and various functional materials. However, the vast majority of these require use a toxic costly catalyst leading unpractical, hazardous often functionally limited conditions. Herein, we report new, general, practical, efficient, mild high-yielding hydrogen-free electrochemical method for reduction alkene, alkyne, nitro azido groups. Finally, this has been applied deuterium labelling.

Язык: Английский

---

Photochemistry in Medicinal Chemistry and Chemical Biology

Journal of Medicinal Chemistry, Год журнала: 2024, Номер 67(6), С. 4322 - 4345

Опубликована: Март 8, 2024

Photochemistry has emerged as a transformative force in organic chemistry, significantly expanding the chemical space accessible for medicinal chemistry. Light-induced reactions enable efficient synthesis of intricate structures and have found applications throughout different stages drug discovery development processes. Moreover, photochemical techniques provide innovative solutions biology, allowing precise spatiotemporal activation targeted delivery. In this Perspective, we highlight already numerous remarkable even more promising future photochemistry chemistry biology.

Язык: Английский

---

Electrocatalytic Hydrogenation Using Palladium Membrane Reactors

JACS Au, Год журнала: 2024, Номер 4(2), С. 328 - 343

Опубликована: Янв. 29, 2024

Hydrogenation is a crucial chemical process employed in myriad of industries, often facilitated by metals such as Pd, Pt, and Ni catalysts. Traditional thermocatalytic hydrogenation usually necessitates high temperature elevated pressure, making the energy intensive. Electrocatalytic offers an alternative but suffers from issues competing H

Язык: Английский

---

Mechanical‐Force‐Induced Non‐spontaneous Dehalogenative Deuteration of Aromatic Iodides Enabled by Using Piezoelectric Materials as a Redox Catalyst

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 30, 2024

Abstract The development of green and efficient deuteration methods is great significance for various fields such as organic synthesis, analytical chemistry, medicinal chemistry. Herein, we have developed a dehalogenative strategy using piezoelectric materials catalysts in solid‐phase system under ball‐milling conditions. This non‐spontaneous reaction induced by mechanical force. D 2 O can serve both deuterium source an electron donor the transformation, eliminating need additional stoichiometric exogenous reductants. A series (hetero)aryl iodides be transformed into deuterated products with high incorporation. method not only effectively overcomes existing synthetic challenges but also used labelling drug molecules derivatives. Bioactivity experiments molecule suggest that D‐ipriflavone enhances inhibitory effects on osteoclast differentiation BMDMs vitro .

Язык: Английский

---