Reactions of ortho-substituted α,α-dibromoacetophenones with nucleophiles: first examples of combined carbophilic and bromophilic attack on C–Br bonds

Tatar, Jovana; Baranac‐Stojanović, Marija; Stojanović, Milovan; Marković, Rade

doi:10.1016/j.tetlet.2008.11.104

Cited by 17 publications

(6 citation statements)

References 31 publications

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“… succeeded in the selective bromination of DHA into 2 and then synthesis of thiazoles 8 by Method I, there has been great demand to develop some alternative approaches for such syntheses avoiding the use molecular bromine and α‐bromoketones because of several practical problems associated with them. In this context, we and other research groups have earlier shown that α,α‐dibromketones behave analogous to α‐bromoketones in their reactions with certain nulceophiles such as sulfur nucleophile and bidentate nucleophiles containing nitrogen and sulfur atoms . These studies involving α,α‐dibromoketones have offered a valuable modification to the most widely used Hantzsch thiazoles synthesis .…”

Section: Introductionmentioning

confidence: 87%

Selective Synthesis of 3‐(α,α‐Dibromoacetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one as an Excellent Precursor for the Synthesis of 2‐Substituted 4‐(4‐Hydroxy‐6‐methyl‐2H‐2‐oxopyran‐3‐yl)thiazoles as Antimicrobial and Antifungal Agents

Kapoor

Prakash

Kumar

et al. 2018

Journal of Heterocyclic Chem

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A selective synthesis of 3-(α,α-dibromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one (3) has been achieved by bromination of DHA using CuBr 2 /CHCl 3 -EtOAc. The reaction of 3 with different thioureas/thiomides/thiosemicarbazide offers a convenient and efficient method for the syntheses of 2-substituted 4-(4-hydroxy-6-methyl-2H-2-oxopyran-3-yl)thiazoles. These thiazoles were evaluated for their antimicrobial and antifungal activity.

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Section: Introductionmentioning

confidence: 87%

Selective Synthesis of 3‐(α,α‐Dibromoacetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one as an Excellent Precursor for the Synthesis of 2‐Substituted 4‐(4‐Hydroxy‐6‐methyl‐2H‐2‐oxopyran‐3‐yl)thiazoles as Antimicrobial and Antifungal Agents

Kapoor

Prakash

Kumar

et al. 2018

Journal of Heterocyclic Chem

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“…Within the literature there exists a plethora of methods that give access to α‐halogenated carbonyl containing species 13 , varying through choice of catalyst or reagent used in the transformation (Scheme 4). [18–25] Due to the similarity of such approaches, we show opposite above a general schematic that represents transformations that involve either the halogenation of methyl ketones, with their respective conditions near the reaction arrows. A single case shows the dehalogenation of a trihalomethyl ketone to access dihaloketone products 13 .…”

Section: Accessing Gem‐difunctionalized Ketones From Carbonyl Substrates and Derivativesmentioning

confidence: 99%

Synthetic Routes Towards the Synthesis of Geminal α‐Difunctionalized Ketones

Day

Vargas

Burtoloso

2021

The Chemical Record

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The importance of gem‐difunctionalized ketones is represented by their broad applications across chemical boundaries over recent years. The interesting reactivities that this class of compounds possess have made them ideal building blocks to access high‐value organic molecules. Furthermore, the gem‐difunctionalized ketone moiety has featured in numerous bioactive molecules. For these reasons, a plethora of routes to access such significant molecules have been developed by research groups worldwide – this account looks at delineating the synthesis of gem‐difunctionalized ketones from carbonyl substrates, diazo compounds, sulfur ylides and alkynyl reactants.

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“…Marchovic and his co‐workers, described the formation of α‐functionalized acetophenones 111 from the corresponding α,α‐dibromocarbonyl compounds 112 by employing various nucleophiles in presence of DMF and H 2 O binary solvent (Scheme ). This process initiated by carbophilic substitution (S N C), followed by bromophilic substitution (S N Br) and finally protonation furnished the α‐substituted acetophenones 111 .…”

Section: αα‐Dihaloketones As Building Blocks In Organic Synthesismentioning

confidence: 99%

The α,α‐Dihalocarbonyl Building Blocks: An Avenue for New Reaction Development in Organic Synthesis

Sadhukhan

Santhi

Baire

2020

Chemistry A European J

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The α,α‐dihalocarbonyl moiety is a bifunctional system with a gem‐dihalocarbon and a carbonyl carbon in 1,2‐fashion. This is one of the privileged scaffolds in medicinal chemistry due to its chemical and metabolic stability and lipophilicity. They have also been found in numerous structurally divergent natural products and most of their fabricated structures have already been in medicinal use. Apart from their important use in medicinal chemistry, the α,α‐dihalocarbonyl groups have been employed as key building blocks for the development of novel synthetic strategies and utilized as intermediates in total synthesis. In addition to the traditional transformations such as oxidations, reductions, and C−C bond formations, recently several new and non‐classical reactions have also been developed. This review provides short description of existing methods for their synthesis and detailed discussion on the efforts for the discovery and development of new reactions by employing α,α‐dihaloketones as synthetic building blocks. We have presented their use as key functional groups for the synthesis of polycyclic systems of medicinal and material importance and natural products.

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Reactions of ortho-substituted α,α-dibromoacetophenones with nucleophiles: first examples of combined carbophilic and bromophilic attack on C–Br bonds

Cited by 17 publications

References 31 publications

Selective Synthesis of 3‐(α,α‐Dibromoacetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one as an Excellent Precursor for the Synthesis of 2‐Substituted 4‐(4‐Hydroxy‐6‐methyl‐2H‐2‐oxopyran‐3‐yl)thiazoles as Antimicrobial and Antifungal Agents

Selective Synthesis of 3‐(α,α‐Dibromoacetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one as an Excellent Precursor for the Synthesis of 2‐Substituted 4‐(4‐Hydroxy‐6‐methyl‐2H‐2‐oxopyran‐3‐yl)thiazoles as Antimicrobial and Antifungal Agents

Synthetic Routes Towards the Synthesis of Geminal α‐Difunctionalized Ketones

The α,α‐Dihalocarbonyl Building Blocks: An Avenue for New Reaction Development in Organic Synthesis

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