Silicon Industry Waste Polymethylhydrosiloxane-Mediated Benzotriazole Ring Cleavage: A Practical and Green Synthesis of Diverse Benzothiazoles

Yadav, Mukesh; Singh, Anoop S.; Agrahari, Anand K.; Mishra, Nidhi; Tiwari, Vinod K.

doi:10.1021/acsomega.9b00343

Cited by 27 publications

(21 citation statements)

References 71 publications

(54 reference statements)

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“…[48] Very recently,t hey demonstrated that the denitrogenative cyclization of N-thioacyl benzotriazoles mediated by industrial waste polymethylhydrosiloxane( PMHS) insteado fnBu 3 SnH provided ag reener approach to synthesize benzothiazoles. [49] Interestingly,t he Bu 3 SnH-mediated ring-opening reaction of N-phenylacylbenzotriazole led to N-phenylbenzamide instead of the cyclization product under free radical conditions. [50] Furthermore, the same group developed aL ewis-acid-mediated system for the ring-cleavage of N-aroylbenzotriazoles 150, which provided an efficient approach for the synthesis of benzoxazoles 151 in 43-91 %y ields (Scheme 27).…”

Section: Denitrogenative Cyclization Of Benzotriazolesmentioning

confidence: 99%

Synthesis of Heterocycles through Denitrogenative Cyclization of Triazoles and Benzotriazoles

Zhang

2020

Chemistry A European J

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During the past few decades, there has been considerable growth in the development of denitrogenative reactions of triazole skeletons to construct valuable cyclic compounds, particularly heterocycles. Despite the inherent difficulty of the ring‐opening of triazole derivatives, many novel and efficient approaches have arisen in this area mainly with the use of transition metal (such as rhodium, palladium, silver, copper) catalysis, photolysis, or free radical mediated reactions. Generally, these procedures begin with the ring‐opening of 1,2,3‐triazoles or benzotriazoles followed by N2 extrusion and subsequent diverse transformations, which enable the rapid synthesis of various heterocycles in a single step. To avoid overlap with other related reviews, this minireview covers the recent advances in the denitrogenative cyclization of 1,2,3‐triazoles since 2016 and the denitrogenative cyclization of benzotriazoles since 2012.

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Section: Denitrogenative Cyclization Of Benzotriazolesmentioning

confidence: 99%

Synthesis of Heterocycles through Denitrogenative Cyclization of Triazoles and Benzotriazoles

Zhang

2020

Chemistry A European J

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“…30 In recent years, benzotriazole derivatives have been employed in inter-and intramolecular cyclizations via a denitrogenative process for the synthesis of various nitrogencontaining fused heterocycles. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] In 2009, Nakamura and co-workers reported a novel route for the palladium-catalyzed denitrogenative [3+2]cycloaddition of N-aroylbenzotriazoles 1 with internal alkynes 2 for the construction of biologically relevant indole derivatives 3 (Scheme 4). 6 Notable advantages of this novel protocol include a simple, solvent-and base-free experimental procedure, mild reaction conditions, easy separation of the product, the release of molecular nitrogen gas as the sole by-product and satisfactory reaction yields.…”

Section: Cyclization Reactionsmentioning

confidence: 99%

“…More recently, we developed a green and efficient modification of this process for the synthesis of benzothiazoles using polymethylhydrosiloxane (PMHS) as the radical reducing agent, instead of Bu 3 SnH and (TMS) 3 SiH (Scheme 37). 16,17 The use of the silicone industry by-product polymethylhydrosiloxane (PMHS) makes the process cost-effective, more practical and greener than the previous BtRC methods as PMHS is a non-toxic and biodegradable industrial waste.…”

Section: Scheme 36 Intramolecular Cyclization Of Benzotriazole Derivamentioning

confidence: 99%

“…[6][7][8][9][10][11][12][13] On the other hand, intramolecular cyclizations for the synthesis of benzothiazoles and benzoxazoles have been recently reported by the Tiwari group. [14][15][16][17][18][19][20][21]…”

Section: Introductionmentioning

confidence: 99%

“…Tiwari's group has performed significant research in this field. [14][15][16][17][18][19][20][21] In 2013, we developed a novel protocol for the synthesis of various benzothiazole glycoconjugates from protected carbohydrates through intramolecular cyclization (Scheme 35). 14 This reaction underwent free radical scission of the N-N bond of the benzotriazole ring by treatment with a stannane under heating or microwave irradiation.…”

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confidence: 99%

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Recent Developments on Denitrogenative Functionalization of Benzotriazoles

Yu¹,

Singh

Yan³

et al. 2020

Synthesis

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Benzotriazoles are employed as useful synthons in organic synthesis, and due to their unique structural motif, they are able to undergo denitrogenation during the construction of new bonds. Various methods for the functionalization of benzotriazoles as precursors of ortho-amino arenediazoniums have recently been developed that involve transition-metal-catalyzed coupling reactions, mainly via cyclization, borylation, alkenylation, alkylation, carbonylation and the formation of carbon–heteroatom bonds. In this short review, we primarily focus on the recent applications of benzotriazoles in organic chemistry that proceed via a denitrogenative process, and the mechanisms are also discussed.1 Introduction2 Common Synthetic Routes Allowing Easy Access to Benzotriazole Derivatives3 Formation of C–C Bonds3.1 Cyclization Reactions3.2 Arylation, Alkenylation, Alkylation and Carbonylation Reactions4 Carbon–Heteroatom Bond Formation5 Miscellaneous Denitrogenative Functionalization6 Conclusions and Future Perspectives

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An efficient catalytic and solvent‐free method for the synthesis of mono‐organofunctionalized polymethylhydrosiloxane derivatives

Gui

Dong

et al. 2023

Polymers for Advanced Techs

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Synthetic reactions with distinctive physicochemical properties and the study of functional groups during synthesis provide an effective way to design polymers on an individual basis. The functionalization of polymethylhydrosiloxane (PMHS) has been performed via hydrosilylation of PMHS with selected alkenes with different active functional groups. In the reaction of PMHS with selected CC bond‐containing olefins in solvent‐free systems, the most efficient catalyst system can be selected to obtain the PMHS reagents to introduce the desired functional groups while generating only regional isomeric products. On‐line real‐time monitoring techniques, in situ Fourier‐transform infrared (FT‐IR), were utilized to determine the chemical reaction rates and reaction conversions for each chemical reaction, and to assess the merits of the reaction systems. In addition, the structures of the functionalized polymers were characterized using FT‐IR spectroscopy, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The kinetic parameters of typical chemical reaction processes were calculated using Kissinger's equation and Ozawa's equation. The comparisons between solvent and solvent‐free systems were carried out under the same conditions, and the statistics revealed that the solvent‐free system was more efficient than its solvent‐based counterpart. This research on the introduction of monofunctional groups into PMHS side chains might pave the way for a variety of diverse functional groups, thus allowing for the further application of PMHS and its derivatives.

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Silicon Industry Waste Polymethylhydrosiloxane-Mediated Benzotriazole Ring Cleavage: A Practical and Green Synthesis of Diverse Benzothiazoles

Cited by 27 publications

References 71 publications

Synthesis of Heterocycles through Denitrogenative Cyclization of Triazoles and Benzotriazoles

Synthesis of Heterocycles through Denitrogenative Cyclization of Triazoles and Benzotriazoles

Recent Developments on Denitrogenative Functionalization of Benzotriazoles

An efficient catalytic and solvent‐free method for the synthesis of mono‐organofunctionalized polymethylhydrosiloxane derivatives

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