{"title":"Transition‐Metal‐Catalyzed α‐Arylation of Enolates","authors":"D. Prim, S. Marque, A. Gaucher, J. Campagne","doi":"10.1002/0471264180.OR076.02","DOIUrl":null,"url":null,"abstract":"The aim of this chapter is to present an up-to-date overview of the transition-metal-catalyzed alpha-arylation of enolates and their derivatives. This chapter discusses the various efforts to develop highly efficient and selective tools for the catalyzed formation of carbon-carbon and carbon-heteroatom bonds. Among the latter, outstanding results have been obtained in the field of soft, non-organometallic nucleophiles. One of the major challenges is the alpha-arylation of soft carbon nucelophiles such as stabilized carbon enolates and related functional groups. Although alpha-carboxylic acids and keto derivatives are prevalent in natural products and are important in the building blocks of various drugs (e.g., anti-inflammatory drugs, anesthetics, etc.), catalytic alpha-arylation of stabilized carbon enolates has only been recently described. Details on early research is given. More recent developments of this method concern not only the use of a large number of related nucleophiles, but also activated benzylic and vinylogous gamma-arylations. Current efforts are mainly devoted to multiple arylation sequences, intramolecular alpha-arylations, and enantioselective alpha-arylation. Because palladium is the transition metal predominantly employed, the chapter focuses on palladium-assisted synthetic transformation, However other catalytic systems such as nickel, copper, and ruthenium-based catalysts are detailed. \n \n \nKeywords: \n \nAlpha-arylation; \nEnolates; \nTransition metal; \nCatalysts; \nPalladium; \nCopper; \nNickel; \nKetones Aldehydes; \nAmides; \nEsters; \nAmino acids; \nNitriles; \nMethylene compounds; \nMechanisms; \nComparison methods; \nExperimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"1 1","pages":"49-280"},"PeriodicalIF":0.0000,"publicationDate":"2012-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"12","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Reactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/0471264180.OR076.02","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 12
Abstract
The aim of this chapter is to present an up-to-date overview of the transition-metal-catalyzed alpha-arylation of enolates and their derivatives. This chapter discusses the various efforts to develop highly efficient and selective tools for the catalyzed formation of carbon-carbon and carbon-heteroatom bonds. Among the latter, outstanding results have been obtained in the field of soft, non-organometallic nucleophiles. One of the major challenges is the alpha-arylation of soft carbon nucelophiles such as stabilized carbon enolates and related functional groups. Although alpha-carboxylic acids and keto derivatives are prevalent in natural products and are important in the building blocks of various drugs (e.g., anti-inflammatory drugs, anesthetics, etc.), catalytic alpha-arylation of stabilized carbon enolates has only been recently described. Details on early research is given. More recent developments of this method concern not only the use of a large number of related nucleophiles, but also activated benzylic and vinylogous gamma-arylations. Current efforts are mainly devoted to multiple arylation sequences, intramolecular alpha-arylations, and enantioselective alpha-arylation. Because palladium is the transition metal predominantly employed, the chapter focuses on palladium-assisted synthetic transformation, However other catalytic systems such as nickel, copper, and ruthenium-based catalysts are detailed.
Keywords:
Alpha-arylation;
Enolates;
Transition metal;
Catalysts;
Palladium;
Copper;
Nickel;
Ketones Aldehydes;
Amides;
Esters;
Amino acids;
Nitriles;
Methylene compounds;
Mechanisms;
Comparison methods;
Experimental procedures