Silver‐Catalyzed Synthesis of Enones/α‐Iodoenones from Tertiary Propargyl Alcohols

Naveen, Naganaboina; Ramesh, Golla; Balamurugan, Rengarajan

doi:10.1002/slct.201903568

Cited by 5 publications

(8 citation statements)

References 101 publications

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“…A combination of a gold catalyst 28 o with copper triflate was also efficient to perform MSR [32] . Further, several silver salts alone, and AgSBF 6 ( 29 b ) was the best, also performed well MSR starting from tertiary propargylic alcohols [33] …”

Section: New Catalytic Systems Leading To αβ‐Unsaturated Carbonyl Dementioning

confidence: 93%

“…[32] Further, several silver salts alone, and AgSBF 6 (29 b) was the best, also performed well MSR starting from tertiary propargylic alcohols. [33] New (iminophosphorane) Ag(I) coordination polymers 29 e proved to be efficient catalyst precursors for MSR and such systems could be recycled several times with only little loss in activity. [34] Further, iminophosphorane-phosphines are good ligands for rhenium complexes, such as 30 b, which afforded MSR for terminal propargylic alcohols into conjugated enals.…”

Section: Metal Catalystsmentioning

confidence: 99%

“…The halogen atoms have been introduced by using Nhalogeno succinimides or by iodine. Some reactions have been performed using only halogenation reagents (entries 1 and 2), [45,46] while in other cases gold catalyst 28 n (entry 3) [47] or silver catalyst 29 b (entry 4) [33] have been employed. Trapping of the intermediate allenol by the electrophilic halogenation agent was a possible mechanism for these transformations.…”

Section: Halogeno-substituted α-Enonesmentioning

confidence: 99%

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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: New Catalytic Systems Leading To αβ‐Unsaturated Carbonyl Dementioning

confidence: 93%

Section: Metal Catalystsmentioning

confidence: 99%

Section: Halogeno-substituted α-Enonesmentioning

confidence: 99%

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Recent Developments in the Meyer‐Schuster Rearrangement

Justaud¹,

Hachem

Grée³

2021

Eur J Org Chem

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“…Except for a trio of examples whose Z/E ratio ranges from 1.2 : 1 to 2.5 : 1, the rest show a parity between the thermodynamic Z-and the kinetic E-isomers (Scheme 18). 28 Attempts to produce a-chloroenone and a-bromoenones from NCS and NBS, respectively, using the same conditions and tertiary propargyl alcohols were unsuccessful. 28 2.2.2 (E)-Haloenones from gold(I), gold(III), and vanadium(V) catalysis 2.2.2.1 With Au(I)-1,2,3-triazole.…”

Section: Introductionmentioning

confidence: 99%

“…28 Attempts to produce a-chloroenone and a-bromoenones from NCS and NBS, respectively, using the same conditions and tertiary propargyl alcohols were unsuccessful. 28 2.2.2 (E)-Haloenones from gold(I), gold(III), and vanadium(V) catalysis 2.2.2.1 With Au(I)-1,2,3-triazole. A high E/Z ratio, in which the kinetic (E)-isomer becomes the dominant product, is elusive.…”

Section: Introductionmentioning

confidence: 99%

Electrophilic halogenations of propargyl alcohols: paths to α-haloenones, β-haloenones and mixed β,β-dihaloenones

2022

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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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Silver‐Catalyzed Synthesis of Enones/α‐Iodoenones from Tertiary Propargyl Alcohols

Abstract: Tertiary propargyl alcohols undergo smooth Meyer-Schuster rearrangement to give enones in the presence of silver catalyst alone at room temperature. The intermediate can be trapped using NIS to make useful tetra substituted α-iodoenones.

Cited by 5 publications

References 101 publications

Recent Developments in the Meyer‐Schuster Rearrangement

Recent Developments in the Meyer‐Schuster Rearrangement

Electrophilic halogenations of propargyl alcohols: paths to α-haloenones, β-haloenones and mixed β,β-dihaloenones

The Meyer–Schuster Rearrangement

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