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

Fen Han

et al.

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

Improved Palladium Catalysis in Suzuki‐Type Coupling of Benzotriazinones for o‐Aryl/Alkenyl Benzamides DOI
Minling Xü, Ke Xü, Gang Zou

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(11), P. 2623 - 2628

Published: April 20, 2024

Abstract A palladium catalyst system based on PdCl 2 (PPh 3 ) or (dppf) is reported for Suzuki‐type coupling of both N ‐aryl and alkyl benzotriazinones with aryl/alkenyl boronic acids to afford a series ortho ‐aryl/alkenyl benzamides in yields up 99%, showing improvements catalytic efficiency, substrate scope practicality. Scope limitations the improved protocol have been demonstrated more than 40 examples, including multigram‐scale synthesis activated o ‐biphenyl amide. Large electronic steric effects from acid counterpart observed, implying transmetallation boron should be involved rate‐determining step cycle.

Language: Английский

Citations

5
Mechanoredox/Nickel Co-Catalyzed Cross Electrophile Coupling of Benzotriazinones with Alkyl (Pseudo)halides DOI
Huimin Wang,

Wenbin Ding,

Gang Zou

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 12891 - 12901

Published: Aug. 24, 2023

An air-tolerant mechanoredox/nickel cocatalyzed cross electrophile coupling of benzotriazinones with alkyl (pseudo)halides is developed by liquid-assisting grinding in the presence manganese powders and strontium titanate as a reductant cocatalyst, respectively. Mechanical activation metal surfaces via ball milling eliminates chemical activator for manganese, while mechanoredox cocatalysis remarkably improves aryl/alkyl piezoelectricity-mediated radical generation from halides. Both display reactivities different those conventional thermal chemistry solution. The scope reaction demonstrated 26 examples, showing high chemoselectivity bromides vs chlorides.

Language: Английский

Citations

12
Recent Advancement in the Conversion of 1,2,3‐Benzotriazin‐4(3H)‐One to Other Heterocyclic Systems and Their Applications: A Concise Review DOI Open Access
Zunera Khalid, Hafiz Adnan Ahmad, Munawar Ali Munawar

et al.

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

Citations

0
Electrochemical Cascade Reactions of 1,2,3-Benzotriazinones with Alkynes to Assemble 3,4-Dihydroisoquinolin-1(2H)-ones DOI

Sanfei Nian,

Xudong Wu,

A. A. Chen

et al.

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

Published: April 21, 2025

An unexpected electrochemical cascade reaction of 1,2,3-benzotriazinones with alkynes to assemble 3,4-dihydroisoquinolin-1(2H)-ones has been developed, which avoids the use pressurized H2, any metal catalysts, and stoichiometric redox agents. This route tolerates a wide range functional groups in both reactants can be performed under an air atmosphere. The process continuous cathodic reduction was demonstrated by control experiments cyclic voltammograms. Moreover, gram-scale confirmed potential this environmentally benign method for practical applications.

Language: Английский

Citations

0
Synthesis of ortho-Methylated Benzamides via Palladium-Catalyzed Denitrogenative Cross-Coupling Reaction of [1,2,3]-Benzotriazin-4(3H)-ones with DABAL-Me3 DOI

Shangzhang Li,

Yang Li,

Riqian Zhu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(29), P. 5443 - 5447

Published: July 13, 2023

We herein developed a palladium-catalyzed reaction of [1,2,3]-benzotriazin-4(3H)-ones with DABAL-Me3 [bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct], cheap, stable, and solid organoaluminum reagent. In the presence Pd(OAc)2/XantPhos as commercially available catalyst, underwent denitrogenative coupling to afford wide array N-aryl amides derived from ortho-methylated carboxylic acids. Under same catalytic conditions, ortho-ethylation could also be achieved by using triethylaluminum.

Language: Английский

Citations

9
Magnesium-Mediated Cross-Electrophile Couplings of Aryl 2-Pyridyl Esters with Aryl Bromides for Ketone Synthesis through In Situ-Formed Arylmagnesium Intermediates DOI
Xiaowei Han, Yuan He,

Chao Gui

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13661 - 13668

Published: Sept. 9, 2024

Aryl 2-pyridyl esters could efficiently undergo cross-electrophile couplings with aryl bromides the aid of magnesium as a reducing metal in absence transition-metal catalyst, leading to unsymmetrical diaryl ketones modest good yields wide functionality compatibility. In addition, reaction be easily scaled up and applied late-stage modification biologically active molecules. Preliminary mechanistic study showed that coupling presumably proceeds through situ formation arylmagnesium reagents key intermediates.

Language: Английский

Citations

3
Rh(III)-Catalyzed Dienylation and Cyclopropylation of 1,2,3-Benzotriazinones with Alkylidenecyclopropanes DOI
Yanzhi Liu, Yao‐Fu Zeng,

Jiaohang Wei

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5179 - 5184

Published: July 6, 2023

Rh (III)-catalyzed dienylation and cyclopropylation of 1,2,3-benzotriazinones with alkylidenecyclopropanes (ACPs) has been achieved. Different from the previous reports 1,2,3-benzotriazinones, triazinone ring remained intact in this C-H bond functionlization reaction. Also, denitrogenative could also be realized by changing reaction temperature. This protocol is featured high E selectivity, wide substrate scope, divergent structures products.

Language: Английский

Citations

7
Enantioselective domino alkyl arylation of vinyl phosphonates by combining photoredox and nickel catalysis DOI Creative Commons

Tingzhi Lin,

Guorong Li, Qianqian Lü

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: April 1, 2024

A nickel/photoredox mediated asymmetric domino alkyl arylation of vinyl phosphonates to generate a diverse array enantioenriched α-aryl is disclosed. This three-component difunctionalization couples aryl halides and bromides with phosphonates, exhibiting excellent chemo- regioselectivity under mild reaction conditions. The method avoids the need for pre-formed organometallics phosphorus halides. Mechanistic DFT studies suggest that photoexcited [4CzIPN]* oxidizes diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate (HEH) [4CzIPN]•–, which then reduces bromide form radicals undergo Giese addition phosphonate. At same time, Ni0 oxidatively adds followed by enantiodetermining oxidative radical trapping phosphonate-based tetrahedral NiII center reductive elimination. Independent gradient model based on Hirshfeld partition (IGMH) analysis suggests orientation phosphonate group (P=O…π interaction) expected play an essential role in controlling enantioselectivity.

Language: Английский

Citations

2
Recent advances in synthesis and transformations of 1,2,3-benzotriazinones DOI
Fatemeh Doraghi, Somaye Karimian, Bagher Larijani

et al.

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 1013, P. 123156 - 123156

Published: April 25, 2024

Language: Английский

Citations

2
Ru(II)-Catalyzed C–H Amination of 1,2,3-Benzotriazinones with Azide Compounds DOI

Han‐Chi Wang,

Quanjian Luo,

Jin‐Heng Li

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12249 - 12254

Published: Aug. 8, 2024

A Ru(II)-catalyzed directed C–H amination of 1,2,3-benzotriazinones with azide compounds has been reported. The reaction a wide substrate scope organic azides good results and represents useful pathway to the construction versatile heterocyclic amino products. In addition, method can be used for phthalazinones, highlighting synthetic practicability strategy.

Language: Английский

Citations

2