Vinylogous Nitro-Haloform Reaction Enables Aromatic Amination

Monasterolo, Claudio; Adamo, Mauro F. A.

doi:10.1021/acs.orglett.2c01494

Cited by 2 publications

(1 citation statement)

References 30 publications

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“…−64 °C). The identification of the chloroform anion as a viable leaving group was essential to the selection of a practical reagent and has its basis spanning nearly a century of heterocycle synthesis [18–21] . This approach allowed for the employment of trichloroacetonitrile as a highly electrophilic partner to trifluoroacetamidine ( 1a ), which is itself a rather poor nucleophile ( Scheme 4).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of Trifluoromethyl‐Substituted 1,3,5‐Triazines

Baiazitov

Chierchia

Niederer

et al. 2023

Helvetica Chimica Acta

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A variety of di‐ and trifluoromethyl‐s‐triazines are prepared following straightforward synthetic protocols from simple, commercially available starting materials. Trichloromethyl‐substituted triazine electrophiles are obtained in good yield and react with amine nucleophiles to afford aminotriazine products in good to excellent yield. The nucleophilic aromatic substitution reaction is broad in scope and proceeds smoothly with both aromatic and aliphatic (primary, secondary, and branched) amines in the presence of non‐participating functional groups including alcohols, carboxylic acids, indoles, and common amine protecting groups. Furthermore, most reactions require only a catalytic amount of 4‐DMAP with no stoichiometric base and are complete within 2 hours at ambient temperature.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of Trifluoromethyl‐Substituted 1,3,5‐Triazines

Baiazitov

Chierchia

Niederer

et al. 2023

Helvetica Chimica Acta

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200 Years of The Haloform Reaction: Methods and Applications

Rowett,

Heard,

Koria

et al. 2024

Chemistry A European J

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Discovered in 1822, the haloform reaction is one of the oldest synthetic organic reactions. The haloform reaction enables the synthesis of carboxylic acids, esters or amides from methyl ketones. The reaction proceeds via exhaustive a‐halogenation and then substitution by a nucleophile to liberate a haloform. The methyl group therefore behaves as a masked leaving group. The reaction methodology has undergone several important developments in the last 200 years, transitioning from a diagnostic test of methyl ketones to a synthetically useful tool for accessing complex esters and amides. The success of the general approach has been exhibited through the use of the reaction in the synthesis of many different complex molecules in fields ranging from natural product synthesis, pharmaceuticals, agrochemicals, fragrants and flavouring. The reaction has not been extensively reviewed since 1934. Therefore, herein we provide details of the history and mechanism of the haloform reaction, as well as an overview of the developments in the methodology and a survey of examples, particularly in natural product synthesis, in which the haloform reaction has been used.

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Vinylogous Nitro-Haloform Reaction Enables Aromatic Amination

Cited by 2 publications

References 30 publications

Synthesis and Reactions of Trifluoromethyl‐Substituted 1,3,5‐Triazines

Synthesis and Reactions of Trifluoromethyl‐Substituted 1,3,5‐Triazines

200 Years of The Haloform Reaction: Methods and Applications

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