Iodine mediated propargylic substitution/aza-Meyer–Schuster rearrangement: stereoselective synthesis of conjugated unsymmetrical azines

Muthusamy, Sengodagounder; Selvaraj, Karuppu; Suresh, Eringathodi

doi:10.1016/j.tetlet.2016.09.055

Cited by 11 publications

(3 citation statements)

References 45 publications

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“…The aza‐MSR has been also performed with isatin hydrazones 296 (Scheme 73). [129] In the presence of iodine in dichloroethane at room temperature, the propargylic alcohol 295 afforded in excellent yields the diazatrienes 297 through the aza ‐MSR followed by tautomerization. When the reaction was performed with an excess of iodine (2.5 equiv), the iodo derivatives 298 were obtained also in good yields.…”

Section: The Aza‐meyer‐schuster Rearrangementmentioning

confidence: 99%

Recent Developments in the Meyer‐Schuster Rearrangement

Justaud¹,

Hachem

Grée³

2021

Eur J Org Chem

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Most of this review article has been prepared during Covid 19 pandemy. Therefore, we dedicate it,-first to all persons who unfortunately died from this disease and,-second to all people (medical doctors and many others) who helped their congeners to survive to this pandemy. The Meyer-Schuster rearrangement is an efficient method to prepare α,β-unsatured carbonyl compounds starting from propargylic alcohols and this review presents the remarkable progress made during the last decade in this reaction. New efficient catalytic systems have been discovered and many elegant applications have been reported for this rearrangement. To be noticed in particular are the new and efficient cascade processes affording a wide range of carbo-and heterocyclic molecules. Moreover, brilliant applications of this rearrangement have been described as well, in the total synthesis of complex natural products and their analogues. Finally, the first examples of aza-Meyer-Schuster rearrangements have been recently described as well.

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Section: The Aza‐meyer‐schuster Rearrangementmentioning

confidence: 99%

Recent Developments in the Meyer‐Schuster Rearrangement

Justaud¹,

Hachem

Grée³

2021

Eur J Org Chem

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“…Muthusamy and co-workers in the year 2016 reported a iodine mediated reaction of propargyl alcohols 39 and isatin hydrazones 315 under open air condition to synthesize highly substituted as well as conjugated unsymmetrical azines 316 in good yield, Scheme 151. 187 Several other Lewis acids like BF 3 $OEt 2 , Yb(OTf) 3 , Sc(OTf) 3 , FeCl 3 and InCl 3 , were found inefficient in catalyzing the reaction. Surprisingly, only DCE was found to the suitable solvent, among several other solvents screened, for this reaction.…”

Section: Iodine Derived Catalystsmentioning

confidence: 99%

Section: Different Catalysts Used In Propargylic Substitution Reactionsmentioning

confidence: 99%

Scope and advances in the catalytic propargylic substitution reaction

2018

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The Meyer–Schuster Rearrangement

Vidari,

Chiodi,

Porta

et al. 2024

Organic Reactions

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The Meyer–Schuster rearrangement corresponds to a formal 1,3‐shift of a propargylic alcohol to afford the corresponding α,β‐unsaturated carbonyl compound via tautomerization of an allenol intermediate. The original acidic and harsh conditions have been replaced with mild and selective conditions that are compatible with a variety of functional and protecting groups. Commonly employed strategies include the activation of propargylic alcohols as esters, transition‐metal catalysis (e.g., gold complexes and oxometal complexes), and the C–H bond activation of terminal propargylic alcohols by transition‐metal insertion. The Meyer–Schuster rearrangement has been extended to all classes of propargylic alcohols and esters, including C sp ‐heteroatom‐substituted alkynols, as well as to propargylic amine derivatives (i.e., the aza‐Meyer–Schuster rearrangement). Moreover, the rearrangement can be employed in inter‐ and intramolecular one‐pot consecutive reactions, wherein multiple carbon–carbon and/or carbon–heteroatom bonds are formed. The Meyer–Schuster reaction exhibits a high atom economy, simple experimental procedures, and good‐to‐excellent product yields and stereoselectivities. Moreover, starting materials are easily accessible, and any toxic metals are employed in substoichiometric amounts. As such, the Meyer–Schuster rearrangement compares favorably with other standard protocols, such as the Wittig reaction, for the preparation of α,β‐unsaturated carbonyl compounds and derivatives. This review covers the literature since the identification of the reaction up to the end of 2020 and includes relevant references through November 2023. Both the mechanistic features and the regio‐ and stereoselectivity issues are discussed as they relate to the reaction conditions. The scope and limitations of the reaction are presented, as are a selection of synthetic applications, several general experimental procedures, and a comparison of the Meyer–Schuster rearrangement with other known methods. Finally, the tabular survey highlights the broad range of starting materials and products possible with the Meyer–Schuster rearrangement.

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Iodine mediated propargylic substitution/aza-Meyer–Schuster rearrangement: stereoselective synthesis of conjugated unsymmetrical azines

Cited by 11 publications

References 45 publications

Recent Developments in the Meyer‐Schuster Rearrangement

Recent Developments in the Meyer‐Schuster Rearrangement

Scope and advances in the catalytic propargylic substitution reaction

The Meyer–Schuster Rearrangement

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