Visible-Light-Induced Defluorinative α-C(sp³)–H Alkylation for the Synthesis of gem-Difluoroallylated α-Trifluoromethylamines

Organic Letters, Год журнала: 2023, Номер 25(51), С. 9124 - 9129

Опубликована: Ноя. 17, 2023

Herein, we describe a novel and efficient photoredox catalytic Cα radical addition/defluoroalkylation coupling reaction between α-trifluoromethyl alkenes N-trifluoroethyl hydroxylamine. A series of gem-difluoroallylated α-trifluoromethylamines were synthesized by the addition enabled 1,2-H shift in situ-generated radical. Notably, this protocol is distinguished its mild conditions, easy operation, excellent functional group tolerability.

Язык: Английский

---

Photoexcited Ni^II–Aryl Complex-Mediated Giese Reaction of Aryl Bromides

Organic Letters, Год журнала: 2023, Номер 25(22), С. 4056 - 4060

Опубликована: Май 31, 2023

A Giese reaction of aryl bromides with electron-deficient alkenes was developed, enabled by a dual catalyst system containing NiII complex and IrIII photocatalyst. This protocol could accommodate variety alkenes, delivering the conjugate adducts in up to 97% yield. The utilization photoexcited (dtbbpy)NiII(aryl)Br intermediate as an radical source allows this novel transformation halides, thus expanding chemical space excited nickel catalysis.

Язык: Английский

---

Photocatalytic C–H Trifluoroethoxylation of (Hetero)arenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

The trifluoroethoxy group (OCH2CF3) is a valuable motif prevalent in pharmaceuticals and agrichemicals. Herein, we present simple radical trifluoroethoxylation method that enables nondirected functionalization of C-H bonds broad array substrates, providing access to (hetero)aryl trifluoroethyl ethers. current protocol tolerates variety synthetically pharmacologically relevant functional groups. Applicability also demonstrated through the late-stage biorelevant molecules marketing drugs.

Язык: Английский

---

Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Язык: Английский

---

Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 6, 2023

The cross-dehydrogenative coupling (CDC) reaction is the most direct and efficient method for constructing α-tertiary amino acids (ATAAs), which avoids pre-activation of C(sp3)-H substrates. However, use transition metals harsh conditions are still significant challenges these reactions that urgently require solutions. This paper presents a mild, metal-free CDC construction ATAAs, compatible with various benzyl C-H substrates, functionalized alkyl good regioselectivity. Notably, our exhibits excellent functional group tolerance late-stage applicability. According to mechanistic studies, one-step synthesized bench-stable N-alkoxyphtalimide generates highly electrophilic trifluoro ethoxy radical serves as key intermediate in process acts hydrogen atom transfer reagent. Therefore, additive-free offers promising strategy synthesis ATAAs under mild conditions.

Язык: Английский

---

Hydroxytrifluoroethylation and Trifluoroacetylation Reactions via SET Processes

Chemistry - A European Journal, Год журнала: 2024, Номер 30(18)

Опубликована: Янв. 6, 2024

Hydroxytrifluoroethyl and trifluoroacetyl groups are of utmost importance in biologically active compounds, but methods to tether these motifs organic architectures have been limited. Typically, the preparation compounds relied on use strong bases or multistep routes. The renaissance radical chemistry photocatalytic, transition metal mediated, hydrogen atom transfer (HAT) processes allowed installation medicinally relevant fluorinated motifs. This review provides an overview available for direct synthesis hydroxytrifluoroethyl- trifluoroacetyl-derived governed by single-electron processes.

Язык: Английский

---

Photocatalytic C(sp³)‐H gem‐Difluoroallylation and Alkylation with Alkenes via a Base‐Assisted Formal 1,2‐Hydrogen Atom Transfer of Amidyl Radicals

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2203 - 2210

Опубликована: Май 14, 2024

Comprehensive Summary Compared to well‐established 1,5‐HAT of N ‐centered radicals, the synthetic applications 1,2‐HAT process were scarce due high barrier and constrained three‐membered transition state. Here, we have developed a novel C(sp 3 )‐H gem ‐difluoroallylation via base assisted formal amidyl radicals with reductive quenching cycle photocatalyst. This transformation enables efficient formation α‐aminoalkyl showcases good functional group tolerance. Our preliminary mechanistic experiments, along Density Functional Theory (DFT) calculations demonstrate feasibility especially when by base. Furthermore, our method also succeeds in Giese addition electron‐deficient alkenes as well styrene.

Язык: Английский

---

Fluoroalkoxylating Reagents in Organic Synthesis: Recent Advances

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(25)

Опубликована: Апрель 22, 2024

Abstract The fluoroalkoxy groups (OR f ) are widely used motifs in pharmaceutical and agrochemical fields due to their unique physicochemical properties including higher lipophilicity increased metabolic stability. Thus, the high value of OR ‐containing derivatives has stimulated development fluoroalkoxylation reactions. In this review, we highlight recent progress various trifluoroalkoxylating reagents applications organic synthesis past five years.

Язык: Английский

---

Ni‐Catalyzed Cross‐Electrophile Couplings of N‐Alkoxyphthalimides and Aryl Halides

European Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 13, 2025

N ‐alkoxyphthalimides represent a versatile class of redox‐active alcohol derivatives for carbon–carbon bond formation following activation by single‐electron reduction. Herein, key precedents using the new bonds under photochemical reaction conditions are first presented. The merger these and other strategies with Ni catalysis in various cross‐electrophile couplings aryl halides is then highlighted. A particular focus made on mechanisms proposed Ni‐catalyzed reductive cross‐couplings. Concluding thoughts future design as C(sp 3 )O transition metal‐catalyzed cross‐couplings also

Язык: Английский

---

Photoexcited Copper-Catalyzed Difunctionalization of Alkenes for the Synthesis of 2,5-Diamino Acid Derivatives via Uncommon 1,2-Hydrogen Atom Transfer of Amidyl Radicals

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 25, 2025

Compared with 1,5-hydrogen atom transfer (1,5-HAT) processes, 1,2-HAT processes have been reported less frequently. And, the synthesis of 2,5-diamino acid derivatives via a mild photocatalytic approach has not yet. Herein, we report photoexcited copper-catalyzed difunctionalization alkenes for uncommon 1,2-HAT. The potential synthetic merit this reaction is proven through scale-up reaction. Notably, new protocol successfully applied to obtain series derivatives.

Язык: Английский

---