[3,3]-Acyloxy Rearrangement-Triggered Regioselective Hydration of δ-Acetoxy-α,β-Alkynoates/Halo Alkynes

Mendhekar, Kishor L.; Pradhan, Tapas R.; Mohapatra, Debendra K.

doi:10.1021/acs.joc.0c00061

Cited by 3 publications

(3 citation statements)

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“…It is not specified whether the double bond of 71 is important for this regioselectivity. The authors proposed a mechanism like that previously evoked by Mohapatra involving a preferential 5- exo - dig cyclization favored by the presence of an electron-withdrawing group attached to the triple bond. Again, the strong polarization of the triple bond generated by the ester linked to Cβ can also be evoked to explain the regioselectivity and the addition of water to Cα.…”

Section: Hydration Of Internal Alkynes Directed By Carbonyl and Phosp...mentioning

confidence: 64%

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Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

et al. 2023

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Water addition on an unsymmetrical internal alkyne has significance in organic chemistry and has stimulated challenging approaches to access a highly regioselective process. Hydration or formal hydration is presented according to the type of internal alkyne. Methods for electron-rich and -poor diarylalkynes followed by those adapted to arylalkylalkynes are presented. Regioselective hydration reactions of unsymmetrical propargylic and homopropargylic derivatives are then discussed, followed by regioselective aspects of the hydration of internal alkynes directed by carbonyl groups. The following section examines the hydration alkynes linked to CF 3 , esters, ketones, and heteroatoms as haloalkynes, alkynylphosphonates, ynamides, and others. At the end of this section, we report some recent examples of hydration reactions where the alkyne triple bond is connected to an electron-withdrawing group as an ester or a ketone. Reactions are presented, discussed, and illustrated in each of these items through various representative examples. The mechanistic hypotheses explaining the origin of the regioselectivity in the hydration reactions are discussed. This review of recent advances in the regioselective hydration of internal unsymmetrical alkynes (from 2007 until the present) aims to update the current body of knowledge and aid researchers working in this field.

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Section: Hydration Of Internal Alkynes Directed By Carbonyl and Phosp...mentioning

confidence: 64%

“…In 2020, Mohapatra reported a formal α-regioselective hydration of homopropargylic esters 55 in the presence of gold catalysts . Optimization of reaction conditions revealed the superiority of PPh 3 AuCl associated with AgSbF 6 as a catalytic system in preparing 1,3-ketoesters 56 (Scheme ).…”

Section: Hydration Of (Homo)propargylic Derivativesmentioning

confidence: 99%

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

et al. 2023

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“…Inspired by this success on directed hydration [31] toward the goal of achieving regioselective syntheses of functionalized β ‐keto esters, very recently, their group [34] have also studied the assisted hydration of δ ‐acetoxy α , β ‐alkynoates 55 by using Au(I)‐catalyst (Scheme 17). After careful screening of reaction parameters, 1 mol% of PPh 3 AuCl, silver salt with SbF 6 counter anion, and 1.5 equiv.…”

Section: Carbonyl Participation In Hydration and Annulation Reactionsmentioning

confidence: 99%

An Overview of Water‐Mediated Alkyne Functionalization by Neighboring Group Participation of Carbonyl Groups

Pradhan

Park

2020

Adv Synth Catal

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Reviewed herein, the progress employing the assistance of a neighboring carbonyl group for alkyne functionalization reactions that are mediated by water. Proper arrangement of these transformations is synthetically worthwhile because it will allow chemists to design straightforward synthetic routes for the construction of complex architectures with perfect regio-and chemoselectivity. Researchers must understand the mechanism before aiming a new idea based on these types of transformations as they proceed through a different way in comparison to the strategies that employ carbonyl groups as a directing group for CÀ H functionalization reactions. In general, an oxygen transposition event occurs in the presence of an alkyne activator. In an aim to expose the molecular diversity that can now be accessed employing intramolecular carbonyl assistance, all the precedents are organized systematically for the first time and can be expected to serve as a comprehensive reference work. Therefore, the key arrangement of this review is schemes accompanied by a concise explanatory text describing both advantages and limitations along with the mechanism. Different transformations are ordered in sections according to the chemical structure of the assisted groups. The overall objective of this review is to promote the application of carbonyl-assisted reactions beyond the methodologies dedicated to the regioselective synthesis of carbonyl derivatives and hence, serving it as a valuable reaction archetype in modern-day research for the synthesis of carbo-and heterocycles.

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Site-selective synthesis of 1,3-dioxin-3-ones via a gold(i) catalyzed cascade reaction

Pedrazzani

Monari

et al. 2020

Chem. Commun.

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[3,3]-Acyloxy Rearrangement-Triggered Regioselective Hydration of δ-Acetoxy-α,β-Alkynoates/Halo Alkynes

Cited by 3 publications

References 72 publications

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

An Overview of Water‐Mediated Alkyne Functionalization by Neighboring Group Participation of Carbonyl Groups

Site-selective synthesis of 1,3-dioxin-3-ones via a gold(i) catalyzed cascade reaction

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