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

Molecules, Journal Year: 2025, Volume and Issue: 30(5), P. 1060 - 1060

Published: Feb. 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.

Language: Английский

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Recent Advancement in the Conversion of 1,2,3‐Benzotriazin‐4(3H)‐One to Other Heterocyclic Systems and Their Applications: A Concise Review

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(5)

Published: Feb. 1, 2025

Abstract The nitrogen containing 1,2,3‐benzotriazin‐4(3 H )‐one is structurally worthwhile system for its notable applications in the synthesis of N─ , O ─ and S─ heterocycles bears pivotal significant usage pharmaceutical industrial chemicals. Today most common items like dyes, cosmetics, sanitizers, insecticides plastics are based on heterocyclic moieties. Different starting materials used industrially formation diverse but a valuable structure to prepare numerous products. These conversions radiation or metal‐catalyzed denitrogenation annulation type reactions provide easy, one‐step atom‐economical route. vast significance their cheap make this subject interesting scientific researchers industrialists. This mini review summarizes recent developments transformation ring various other structures phenanthridinones, isoquinolones, coumarin‐1‐imines, benzamides, pyrroloquinazolinones, indolin‐1‐ones, 1,2‐benzisoselenazol‐3(2 )‐ones benzofuranones. Some emerging drugs ebselen, losartan, irbesartan, luotonin A, deoxyvasicinone mackinazolinone have been successfully synthesized from differently substituted benzotriazinones.

Language: Английский

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Synthesis of N-Aryl and N-Alkyl Phthalimides via Denitrogenative Cyanation of 1,2,3-Benzotriazin-4(3H)-ones

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

An efficient metal-free approach for synthesizing N-aryl- and N-alkyl phthalimide derivatives from 1,2,3-benzotriazin-4(3H)-ones is described. The reaction likely proceeds via a denitrogenative cyanation pathway, utilizing TMSCN as the cyanide source. This method straightforward well scalable supports wide range of substrates with high functional group tolerance, yielding diverse in good to excellent yields. utility this further highlighted by successful synthesis tyrosinase inhibitor analogue yield.

Language: Английский

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Iodide/Nickel Co-Catalyzed Manganese-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Alkyl Sulfonates

Molecules, Journal Year: 2025, Volume and Issue: 30(11), P. 2397 - 2397

Published: May 30, 2025

An efficient Ni-catalyzed, Mn-mediated denitrogenative cross-electrophile coupling of N-alkyl-1,2,3-benzotriazinones with alkyl tosylates and mesylates for access to o-alkyl secondary benzamides is reported. The method uses inexpensive non-anhydrous dimethyl acetamide (DMA) in combination tetrabutyl ammonium iodide (TBAI) as a co-catalyst convert sulfonates into iodides situ. Scope limitations the protocol have been demonstrated by >30 examples yields up 91%, showing large electronic effect from N-substituent benzotriazinones. unexpected steric acceleration has observed core benzotriazinones, not only promising highly 2-alkyl-2,3-disubstituted but also shedding light on rate-limiting steps catalytic cycle.

Language: Английский

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A sequential olefin hydroboration/Suzuki coupling for denitrogenative alkylation of benzotriazinones with α-olefins

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 1022, P. 123383 - 123383

Published: Sept. 21, 2024

Language: Английский

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Photoredox Catalyzed Tandem Denitrogenative [4 + 2] Annulation of 1,2,3-Benzotriazin-4(3H)-ones with Terminal Olefins

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 16043 - 16048

Published: Oct. 15, 2024

The dihydroisoquinolones skeleton is ubiquitous in natural products and biological molecules. Reported strategies for constructing usually require noble metal catalysts or stoichiometric oxidants, which limit their wide applications. Herein, we developed a photoredox catalyzed tandem denitrogenative [4 + 2] annulation reaction of 1,2,3-benzotriazin-4(3H)-ones with terminal olefins. A variety can be accessed moderate to excellent yield. This protocol features high atom-economy, mild conditions, external oxidant-free, enabling the synthesis various substituted dihydroisoquinolones.

Language: Английский

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