Lewis Acid-Driven Meyer–Schuster-Type Rearrangement of Yne-Dienone

Mallick, Rajendra K.; Vangara, Srinivas; Kommu, Nagarjuna; Guntreddi, Tirumaleswararao; Sahoo, Akhila K.

doi:10.1021/acs.joc.1c00290

Cited by 9 publications

(2 citation statements)

References 53 publications

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“…All reactions and manipulations involving air-sensitive compounds were performed using the standard Schlenk techniques. Alkyne-tethered cyclohexadienones 1 were prepared according to reported methods. , All other reagents were purchased from commercial sources and used without further purification. Melting points were measured on an SGW @ X-4B apparatus and uncorrected.…”

Section: Methodsmentioning

confidence: 99%

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Huang,

Yi,

Bai

et al. 2024

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Huang,

Yi,

Bai

et al. 2024

J. Org. Chem.

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“…Thus, we have to preliminary conclude here that NaBH 4 is able to hydrogenate the alkene group in 14 by its own, which constitutes a practical reaction (hydrogenation of alkenes with NaBH 4 ) with any uncatalyzed precedent, as far as we know 45 . This methodology adds to related synthetic strategies, such as the circumvention of carbonyl group reduction challenges under Luche reduction 46 . Notice here that racemic 1,2-diarylethanols can be easily converted to enantiomerically pure compounds by dynamic kinetic resolution 47 , thus enabling the access to the corresponding enantiomeric forms of (±)-1.…”

Section: Completion Of the Synthesismentioning

confidence: 99%

Soluble individual metal atoms and ultrasmall clusters catalyze key synthetic steps of a natural product synthesis

Rodríguez-Nuévalos,

Espinosa,

Leyva-Pérez

2024

Commun Chem

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Metal individual atoms and few-atom clusters show extraordinary catalytic properties for a variety of organic reactions, however, their implementation in total synthesis of complex organic molecules is still to be determined. Here we show a 11-step linear synthesis of the natural product (±)-Licarin B, where individual Pd atoms (Pd1) catalyze the direct aerobic oxidation of an alcohol to the carboxylic acid (steps 1 and 6), Cu2-7 clusters catalyze carbon-oxygen cross couplings (steps 3 and 8), Pd3-4 clusters catalyze a Sonogashira coupling (step 4) and Pt3-5 clusters catalyze a Markovnikov hydrosylilation of alkynes (step 5), as key reactions during the synthetic route. In addition, the new synthesis of Licarin B showcases an unexpected selective alkene hydrogenation with metal-free NaBH4 and an acid-catalyzed intermolecular carbonyl-olefin metathesis as the last step, to forge a trans-alkene group. These results, together, open new avenues in the use of metal individual atoms and clusters in organic synthesis, and confirm their exceptional catalytic activity in late stages during complex synthetic programmes.

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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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Lewis Acid-Driven Meyer–Schuster-Type Rearrangement of Yne-Dienone

Cited by 9 publications

References 53 publications

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Soluble individual metal atoms and ultrasmall clusters catalyze key synthetic steps of a natural product synthesis

The Meyer–Schuster Rearrangement

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