Scalable Flow Electrosynthesis of Iminophosphoranes

Organic Process Research & Development, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

A scalable electrochemical process to synthesize iminophosphorane ligands is reported. The application of these iminophosphoranes was recently reported in Ni-catalyzed cross-electrophile and C–N cross-couplings. use parallel plate flow reactors enables the synthesis on a multigram scale, with selected examples up 0.6 kg scale. Direct crystallization from end reaction mixture for provides facile isolation processes. This article also details improvements our capabilities across scales, including addressing material compatibility issues, increasing accessible range rates, integration analytical technology tools.

Язык: Английский

---

Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides

Molecules, Год журнала: 2025, Номер 30(5), С. 1060 - 1060

Опубликована: Фев. 26, 2025

An efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant DMF assisting liquid in the presence anhydrous calcium chloride. Scope limitations protocol to access diarylmethanes have demonstrated more than 20 examples, showing acceptable tolerance functional group steric hindrance. Although electron-withdrawing substituents on benzotriazinone or counterparts decrease yields significantly, a series N-alkyl-2-benzylbenzamides, bearing an ortho-carbamoyl aryl group, could be obtained modest good yields.

Язык: Английский

---

Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Triflates with Alkyl Halides: Mechanism-Informed Design of More General Conditions

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

Aryl triflates make up a class of aryl electrophiles that are available in single step from the corresponding phenol. Despite known reactivity nickel complexes for C-O bond activation phenol derivatives, nickel-catalyzed cross-electrophile coupling using has proven challenging. Herein, we report method to form C(sp2)-C(sp3) bonds by with alkyl bromides and chlorides phenanthroline (phen) or pyridine-2,6-bis(N-cyanocarboxamidine) (PyBCamCN)-ligated catalysts. The scope reaction is demonstrated 38 examples (61 ± 14% average yield). Mechanistic studies provide rationale conditions used roadmap further applications coupling. First, rate radical generation controlled maintaining majority halide as chloride, which unreactive, utilizing dynamic exchange process adjust concentration reactive bromide iodide. Second, challenge electron-rich appears be due off-cycle transmetalation unproductive zinc reagents. optimal PyBCamCN ligand together LiCl avoids this deleterious step.

Язык: Английский

---

One-Pot Chlorination and Cross-Electrophile Coupling of Alcohols with Aryl Chlorides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Although alkyl alcohols and aryl chlorides are the two most abundant substrate pools for cross-electrophile coupling, methods to couple them remain limited. Herein we demonstrate a simple procedure in situ deoxychlorination of followed by XEC with chlorides. A broad scope can be achieved tuning rate reaction via halide exchange. Key success is identification 1-chloro-N,N,2-trimethyl-1-propenylamine as mild, noninterfering halogenation reagent.

Язык: Английский

---

Zn-promoted Sandmeyer-type reductive chalcogenation of (hetero)aryl diazonium salts

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In this report, we describe a nickel-free, zinc-induced reductive coupling between (hetero)aryl diazonium salts and electrophilic chalcogen species under mild reaction conditions.

Язык: Английский

---

C−P Bond Formation by Nickel or Cobalt Catalyzed Coupling Reactions

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract This review discloses nickel‐ and cobalt‐catalyzed coupling reactions that allow C−P bond formation. Activation of C−halide bonds to form phosphonium, pentavalent phosphorus, or trivalent phosphorous compounds has been reported with both metals. However, the conversion C−O ((activated) ethers, carbonates, acetates) into ones only described Ni. Similarly, there are more examples C−Y (Y=C, S, N, B) activations catalyzed by Ni than Co. Nevertheless, cross‐dehydrogenative reaction between a P−H reagent C−H often cobalt nickel. In addition, for metals, electrolytic photocatalytic processes have shown produce variety containing molecules. aims provide an overview potential metals formation highlight remaining challenges.

Язык: Английский

---

Cross-Electrophile Coupling to Form Sterically Hindered C(sp²)–C(sp³) Bonds: Ni and Co Afford Complementary Reactivity

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

The formation of sterically hindered C(sp2)-C(sp3) bonds could be a useful synthetic tool but has been understudied in cross-electrophile coupling. Here, we report two methods that couple secondary alkyl bromides with aryl halides contain C-X bonds: 1) ortho-substituted nickel catalysts and 2) di-ortho-substituted iodides cobalt catalysts. Stoichiometric experiments deuterium labeling studies show [Co] is better than [Ni] for oxidative addition Ar-I radical capture/reductive elimination steps arenes. For both metals, Ar-H side products observed reactions low-yielding appear to arise from Ar• hydrogen-atom transfer the solvent. While origins differences scope are not yet understood, these demonstrate previously unknown complementarity between

Язык: Английский

---

Nickel-catalyzed reductive alkynylation of ketoimines via unstrained C–C bond activation

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111050 - 111050

Опубликована: Март 1, 2025

Язык: Английский

---

Nickel‐Catalyzed Asymmetric Reductive 1,4‐ and 1,5‐Dicarbofunctionalization^†

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 8, 2025

Comprehensive Summary Herein, we present the first examples of asymmetric reductive 1,4‐dicarbofunctionalization 1,3‐dienes and 1,5‐dicarbofunctionalization vinylcyclopropanes, which proceed under catalysis a chiral nickel/bis‐imidazoline complex using alkyl halides aryl iodides or alkenyl bromides as electrophilic coupling partners. In these highly enantioselective transformations operating in radical relay mechanism, C(sp 3 )‐ 2 )‐type carbo‐moieties are respectively installed on terminal internal position with newly formed olefinic unit high E ‐selectivity.

Язык: Английский

---

Nickel-Catalyzed Reductive Arylation of gem-Bromofluorocyclopropanes To Construct Monofluorinated Cyclopropane Derivatives

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

A nickel-catalyzed reductive cross-coupling of gem-bromofluorocyclopropanes with aryl bromides for the synthesis monofluorinated cyclopropane derivatives is reported. Different from cleavage route ring reported by previous works, this catalytic system shows excellent regioselectivity control cyclic selectivity, giving as major product. This transformation demonstrates mild conditions, high efficiency, a broad substrate scope, and good functional group compatibility, providing facile method diversified cyclopropane-containing drugs bioactive molecules.

Язык: Английский

---