Brønsted acid promoted nucleophilation of propargylic alcohols during the Meyer-Schuster rearrangement (M-S) has been introduced. A novel concept of reverse polarization of the M-S intermediate allenyl cation has been realized by employing a cis-enoate assisted strategy. This idea is well demonstrated by the metal free synthesis of complex, highly functionalized cyclic as well as acyclic α-arylenones. The synthetic importance of the derived products was highlighted by the efficient conversion to biologically relevant molecules such as pyrazoles and 4,5-seco-abietane. © The Royal Society of Chemistry 2016.

Beeraiah Baire

Department Of Chemistry

Prabhakararao Tharra

4,5 SECO ABIETANE

abietane derivative

alcohol derivative

ALPHA ARYLENONE ESTER DERIVATIVE

ester derivative

nucleophile

PROPARGYLIC ALCOHOL DERIVATIVE

pyrazole derivative

unclassified drug

article

chemical reaction

electrophilicity

MEYER SCHUSTER REARRANGEMENT

nucleophilicity

Polarization

synthesis

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IIT Madras

Chemical Communications

The Meyer–Schuster rearrangement of propargylic alcohols is a transformation in organic synthesis known for almost a century. The products of this reaction—α,β-enones and their α-functionalized units—are highly important functional groups for various synthetic transformations. Two modifications of this classical reaction, which involves interception of the intermediate allenol (or its equivalent) by either electrophiles or nucleophiles, have attracted the attention of synthetic organic chemists. This Focus Review provides a detailed description of the development of these two strategies. © 2018 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim

Asian Journal of Organic Chemistry

Intercepted Meyer–Schuster Rearrangements in Organic Synthesis

The unconventional reactivity of (Z)-enoate-attached propargylic alcohols in the presence of acids (nucleophilic and non-nucleophilic) was described. This study led to the discovery and development of a new strategy for the collective synthesis of the synthetically useful building blocks α-OMs-, α-OTs-, and α-Cl-enones, as well as 4,5-dioxonoates. The reaction proceeded under very mild conditions and showed a broad substrate scope. © 2017 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim

Chemistry - A European Journal

Unconventional Reactivity of (Z)-Enoate Propargylic Alcohols in the Presence of Acids

A Regioselective and efficient synthesis of α,α-diiodo-α′-acetoxyketones as well as α,α-dibromo-α′ -acetoxyketones has been achieved from the propargylic acetates and N-iodo(bromo)succinimides in the absence of any added promoters. This transformation is very general and shown compatibility for all structural types of propargylic acetates with terminal alkyne unit, such as tertiary- (aryl-aryl; aryl-alkyl; alkyl-alkyl), secondary- (aryl; alkyl), primary-; and hence provided access to structurally divergent and highly important halogenated building blocks. © 2017 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim

ChemistrySelect

An Expeditious Approach to α,α-Dihalo-α′-acetoxyketones from Propargylic Acetates

An acid promoted, unprecedented cascade [3+2] annulation strategy for the synthesis of complex naphtho- and benzofurans is reported. An alkoxyfuranylallene intermediate (generated from Z-enoate propargylic alcohols via a Meyer-Schuster rearrangement) was employed as the 1,2-bis-electrophile and β-naphthols (phenols) as 1,3-bisnucleophiles. This strategy represents the first cascade and metal free process for the synthesis of naphthofurans and benzofurans from propargylic alcohols. A very broad substrate scope was observed. The synthesized naphtho- and benzofurans were efficiently transformed into the frameworks of the bioactive natural products amycofuran and frondosin B. © The Royal Society of Chemistry.

Regioselective, cascade [3+2] annulation of β-naphthols (resorcinols) with Z-enoate propargylic alcohols: a novel entry for the synthesis of complex naphtho(benzo)furans

What is this thing called Philosophy?

do we have any knowledge?

Gallium(III)- and calcium(II)-catalyzed Meyer–Schuster rearrangements followed by intramolecular aldol condensation or endo-Michael addition

Journal of the American Chemical Society

Contemporaneous Dual Catalysis by Coupling Highly Transient Nucleophilic and Electrophilic Intermediates Generated in Situ

Angewandte Chemie International Edition

Gold-Catalyzed Homogeneous Oxidative Cross-Coupling Reactions

The Journal of Organic Chemistry

Controllable One-Step Synthesis of Spirocycles, Polycycles, and Di- and Tetrahydronaphthalenes from Aryl-Substituted Propargylic Alcohols

The: Z -enoate assisted, Meyer-Schuster rearrangement cascade: Unconventional synthesis of α-arylenone esters

Journal	Data powered by TypesetChemical Communications
Publisher	Data powered by TypesetRoyal Society of Chemistry
ISSN	13597345
Open Access	No