アリールテトラゾールの光活性化：反応性ベースの応用によるニトリルイミン運命の制御

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Updated: Feb 27, 2026

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Published on: June 20, 2014

Liu Yang¹, Huilin Yang¹, Yi-Xiang Li¹

¹School of Chemical Science and Technology, Yunnan University, Kunmimg, China.

Chemical record (New York, N.Y.)

|February 26, 2026

Abstract:

Photoactivation of aryl tetrazoles represents a powerful strategy for the spatiotemporally controlled generation of nitrile imines (NIs), highly reactive 1,3-dipoles formed via photolytic cycloreversion with concomitant nitrogen extrusion. These transient intermediates exhibit versatile reactivity, engaging in various transformations through both intermolecular and intramolecular pathways including dipolar cycloadditions and nucleophilic additions. Each specific pathway and efficiency is critically governed by the reaction environments: the presence (or strategic design) of suitable interception partners or tethered functional groups. This review systematically outlines the fundamental reactivity of photogenerated NIs in a spatiotemporally controlled manner and emphasizes strategic control over their reaction pathways. Furthermore, it highlights their advanced applications, spanning photochemical biological labeling, protein manipulation, high-resolution bioimaging, photo-responsive polymers, and material surface engineering. By connecting fundamental principles with diverse applications, this work aims to offer a comprehensive perspective on harnessing the reactivity of photogenerated nitrile imines for precision synthesis and functional material design.

キーワード:

生体共役分子間/分子内環化付加ニトリルイミン 1,3-双極子光化学反応高分子修飾

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Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

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Preparation of Nitriles

Preparation of Nitriles

One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic S_N1

Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...

Nucleophilic Aromatic Substitution: Elimination–Addition

Nucleophilic Aromatic Substitution: Elimination–Addition

Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...

Electrophilic Aromatic Substitution: Nitration of Benzene

Electrophilic Aromatic Substitution: Nitration of Benzene

The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO₂ Mechanism

Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.

Preparation of Amines: Reduction of Amides and Nitriles

Preparation of Amines: Reduction of Amides and Nitriles

Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...