Organic Reactions最新文献

{"title":"Transition-Metal-Catalyzed Hydroacylation","authors":"V. Dong, Kevin G. M. Kou, Diane N. Le","doi":"10.1002/0471264180.OR096.02","DOIUrl":"https://doi.org/10.1002/0471264180.OR096.02","url":null,"abstract":"","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"151 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2018-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77490376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enantioselective, Rhodium-Catalyzed 1,4-Addition of Organoboron Reagents to Electron-Deficient Alkenes","authors":"A. R. Burns, H. Lam, I. D. Roy","doi":"10.1002/0471264180.OR093.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR093.01","url":null,"abstract":"The rhodium-catalyzed 1,4-addition of organoboron reagents to electron-deficient alkenes is a versatile method for the enantioselective construction of carbon–carbon bonds. The scope of these reactions is broad, and alkenes activated by adjacent carbonyls, imines, nitriles, phosphonyl groups, nitro groups, sulfonyl groups, C=N-containing aromatic heterocycles, electron-deficient arenes, or boryl groups are effective substrates. Regarding the pronucleophilic component, aryl-, heteroaryl-, and alkenylboron reagents have been successfully employed. In addition, numerous chiral ligands have been developed which impart high enantioselectivities onto these reactions. Importantly, these reactions usually proceed under mild, experimentally convenient conditions, with no requirement for precautions to exclude air or moisture. \u0000 \u0000 \u0000 \u0000This chapter presents the scope and limitations of this process, along with a discussion of the current understanding of the mechanistic and stereochemical features. Incorporation of this process into domino reactions is discussed, as is its application in the synthesis of biologically active molecules. The literature is covered up until the end of 2013. \u0000 \u0000 \u0000Keywords: \u0000 \u0000alkene; \u0000asymmetric catalysis; \u0000chiral ligand; \u0000enantioselectivity; \u0000organoboron reagent; \u0000rhodium","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"42 1","pages":"1-415"},"PeriodicalIF":0.0,"publicationDate":"2017-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84695465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gold‐Catalyzed Cyclizations of Alkynes with Alkenes and Arenes","authors":"A. Echavarren, Michael E Muratore, Verónica López‐Carrillo, Ana Escribano-Cuesta, N. Huguet, C. Obradors","doi":"10.1002/0471264180.OR092.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR092.01","url":null,"abstract":"This chapter reviews the gold-catalyzed cyclization reactions of alkynes with alkenes that proceed via selective activation of the alkyne by π-coordination of the transition metal. Mechanistically related intermolecular reactions between alkynes and alkenes are also discussed, as are reactions of alkynes with arenes, heteroarenes, and related nucleophiles. \u0000 \u0000 \u0000Keywords: \u0000 \u0000gold; \u0000alkynes; \u0000alkenes; \u0000cyclizations; \u0000skeletal rearrangements; \u0000metal carbenes","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"13 1","pages":"1-288"},"PeriodicalIF":0.0,"publicationDate":"2017-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88449882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cyclization of Vinyl and Aryl Azides into Pyrroles, Indoles, Carbazoles, and Related Fused Pyrroles","authors":"W. F. Berkowitz, S. McCombie","doi":"10.1002/0471264180.OR092.02","DOIUrl":"https://doi.org/10.1002/0471264180.OR092.02","url":null,"abstract":"This chapter reviews in detail those reactions that form of a new pyrrole ring from vinyl, aryl, and heteroaryl azides via formal C–H insertion processes under thermal, photochemical, and metal-catalyzed conditions. These reactions proceed via the intermediacy of vinyl or aryl nitrenes (or their metallonitrene equivalents) and generate a wide variety of pyrroles, indoles, carbazoles, and related systems. Methods for the synthesis of the starting azides are summarized, and a comprehensive survey of the cyclization processes is provided. \u0000 \u0000 \u0000Keywords: \u0000 \u0000pyrrole; \u0000indole; \u0000carbazole; \u0000azidoalkene; \u0000azidoarene; \u0000vinyl nitrene; \u0000aryl nitrene; \u0000thermolysis; \u0000photolysis; \u0000metal catalysis; \u0000C–H functionalization; \u0000nitrene; \u00002-azidostyrene; \u00002-azidobiphenyl","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"34 1","pages":"1-170"},"PeriodicalIF":0.0,"publicationDate":"2017-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83207765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nucleophilic Additions of Perfluoroalkyl Groups","authors":"P. Beier, M. Zibinsky, G. Prakash","doi":"10.1002/0471264180.OR091.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR091.01","url":null,"abstract":"The trifluoromethyl and perfluoroalkyl functional groups possess significant thermal, chemical, and metabolic stability, as well as high lipophilicity and electronegativity. These physicochemical properties render fluorinated carbon residues indispensable in diverse applications, such as agrochemistry, drug design, and material chemistry. The generation and properties of nucleophilic perfluoroalkyl reagents as well as the scope and limitations of their additions to various electrophilic partners is described in this chapter. \u0000 \u0000 \u0000Keywords: \u0000 \u0000fluorine; \u0000trifluoromethyl; \u0000perfluoroalkyl; \u0000nucleophilic addition","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"61 1","pages":"1-492"},"PeriodicalIF":0.0,"publicationDate":"2016-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88572391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Catalytic, Enantioselective Michael Reaction","authors":"Efraím Reyes, U. Uria, J. Vicario, L. Carrillo","doi":"10.1002/0471264180.OR090.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR090.01","url":null,"abstract":"The catalytic enantioselective Michael reaction is the conjugate addition of a resonance-stabilized carbanion to an electron-poor olefin (an αβ-unsaturated carbonyl compound or a related derivative) mediated by substoichiometric amounts of a chiral catalyst that enables stereocontrol in the newly generated stereocenter(s). This reaction allows the direct enantioselective construction of substituted 1,5-dicarbonyl compounds or related architectures through the appropriate selection of the enolizable carbonyl compound employed as pronucleophile and the Michael acceptor. A variety of catalyst architectures have been described that make it possible to carry out this reaction with superior levels of chemical efficiency and high enantio- and stereocontrol, and also under conditions that tolerate a wide variety of functional groups. Both transition metal catalysis and organocatalysis have been employed as methodological approaches for carrying out this reaction in an enantioselective manner. \u0000 \u0000 \u0000 \u0000This chapter describes different catalytic systems and methods developed for achieving enantioselective Michael reactions through the end of 2012, including a detailed mechanistic explanation of the different generic modes of substrate activation operating with each type of catalyst and their associated stereochemical aspects. The intention is to provide researchers interested in applying this methodology to their own synthetic strategies with a suitable starting point for identifying an efficient synthetic approach. In addition, the preparation of selected catalysts that are excellent for a particular pairing of substrates in this reaction, together with practical experimental protocols are described and some examples in which these methodologies have been applied to total synthesis have been included. This chapter is limited exclusively to those examples in which the final Michael addition product is obtained after protonation of the conjugate addition intermediate and therefore, tandem, domino, or cascade processes initiated by Michael reactions lie outside the scope of this work. \u0000 \u0000 \u0000 \u0000Supplemental references are provided for articles published after the 2012 cut-off date through the first half of 2015. \u0000 \u0000 \u0000Keywords: \u0000 \u0000asymmetric synthesis; \u0000carbanions; \u0000catalysis; \u0000conjugate addition; \u0000Michael reaction","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"9 4","pages":"1-898"},"PeriodicalIF":0.0,"publicationDate":"2016-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91549974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Olefin Ring‐Closing Metathesis","authors":"L. Yet","doi":"10.1002/0471264180.OR089.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR089.01","url":null,"abstract":"The olefin ring-closing metathesis reaction catalyzed by ruthenium and molybdenum complexes has been employed in the syntheses of carbocycles, heterocycles, supramolecular compounds, and in tandem metathesis reactions. Chiral ruthenium and molybdenum catalysts have provided high enantiomeric and diastereomeric excesses in ring-closing metathesis reactions. Many of the unsuccessful medium- and large-sized ring formations which were unsuccessful by traditional methods, such as the intramolecular Wittig, Horner–Wadsworth–Emmons, and Julia–Kocienski reactions, can now be formed by olefin ring-closing metathesis reactions. Ring-closing metathesis has been a key step and sometimes the only successful method for the synthesis of numerous natural products and drug discovery targets. The objective of this chapter is to provide an updated, comprehensive coverage of the literature of the olefin ring-closing metathesis reaction and related processes. Key mechanistic points are summarized. \u0000 \u0000 \u0000Keywords: \u0000 \u0000ring-closing metathesis; \u0000Grubb's catalyst; \u0000Schrock's catalyst; \u0000dienes; \u0000asymmetric catalyst; \u0000ruthenium complex; \u0000molybdenum complex; \u0000medium- and large-sized rings; \u0000natural products","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"67 1","pages":"1-1304"},"PeriodicalIF":0.0,"publicationDate":"2016-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81176383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydroamination of Alkenes","authors":"A. Reznichenko, K. Hultzsch","doi":"10.1002/0471264180.OR088.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR088.01","url":null,"abstract":"The addition of an amine NH-functionality to alkenes (including vinyl arenes, conjugated dienes, allenes or ring-strained alkenes), the so-called hydroamination, represents a simple and highly atom-economical approach for the synthesis of nitrogen-containing products. A large variety of catalyst systems are available, ranging from alkali, alkaline earth, rare earth, Group 4 and Group 5 metals, to late transition metal catalysts, and, less prominent, Bronsted and Lewis acid-based catalyst systems. The mode of operation of these catalyst systems can vary significantly and the different reaction mechanisms and the scope and limitations are discussed. While intramolecular hydroamination reactions can be readily achieved with a large number of catalyst systems, significantly fewer examples for the more challenging intermolecular hydroamination are known, especially for unactivated alkenes. The stereoselective hydroamination has also received significant attention due to the importance of chiral nitrogen-containing molecules in pharmaceutical industry. A variety of highly selective chiral catalyst systems have been developed for intramolecular hydroaminations, while examples of intermolecular asymmetric hydroaminations are scarce. \u0000 \u0000 \u0000 \u0000Hydroamination in the context of this review article is defined as the addition of HNR2 across a non-activated, unsaturated carbon-carbon multiple bond. This review focuses on the hydroamination reaction of simple, non-activated alkenes. The addition of amines to slightly activated alkenes, such as vinyl arenes, 1,3-dienes, strained alkenes (norbornene derivatives, methylenecyclopropenes) and allenes is closely related and is covered as well. However, hydroamination reactions of alkynes and Aza-Michael reactions involving the addition of an N-H fragment across the conjugated or otherwise activated double bond of a Michael acceptor are not covered. The scope of amine types includes ammonia, primary and secondary aliphatic and aromatic amines, azoles, and hydrazines. N-Protected amines, such as ureas, carboxamides, and sulfonamides are covered as well, as they are important substrates for metal-free and late transition metal-based catalysts. The literature through January 2011 will be covered with two selected references from 2012 (comprising Table 3D). A supplemental reference list is provided for reports appearing February 2011 through April 2015. \u0000 \u0000 \u0000 \u0000The chapter is organized by the nature of the carbon unsaturation to which the amine is added. Ranging from less reactive substrates such as ethylene and unactivated alkenes, to slightly activated substrates, such as vinyl arenes, and more activated substrates, including conjugated dienes, allenes and strained alkenes. Enantioselective hydroamination reactions, an area that has seen significant progress over the past decade, are discussed next. Finally, tandem hydroamination/carbocyclization reactions of aminodialkenes provide rapid access to complex alkaloidal skeleto","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"41 1","pages":"1-554"},"PeriodicalIF":0.0,"publicationDate":"2015-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77079900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbozincation Reactions of Carbon–Carbon Multiple Bonds","authors":"G. Sklute, Hannah Cavender, I. Marek","doi":"10.1002/0471264180.OR087.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR087.03","url":null,"abstract":"This review summarizes the field of carbozincation of alkenes and alkynes. It includes uncatalysed-, catalyzed-, and promoted-addition of orgnozinc derivatives across the unsaturated bond in alkenes and alkynes. For each reaction, the scope and limitations are discussed with specific emphasis on mechanism and stereochemistry. Experimental conditions and procedures are also presented. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Addition; \u0000alkenes; \u0000alkynes; \u0000carbozincation; \u0000carbon-carbon bond formation; \u0000catalysis; \u0000organozinc","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"6 1","pages":"507-764"},"PeriodicalIF":0.0,"publicationDate":"2015-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82433277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidative Cleavage of Furans","authors":"P. Merino","doi":"10.1002/0471264180.OR087.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR087.01","url":null,"abstract":"Oxidative ring cleavage reactions of furans constitute a group of important transformations that have found wide utility in synthetic organic chemistry. These processes have been used to prepare a variety of 1,4-dicarbonyl compounds including 1,4-dioxoalkenes, 4-oxoalkenals, 4-oxoalkenoic acids, and their derivatives such as 4-hydroxybutenolides and 2,5-dialkoxydihydrofurans. Oxidations of furfuryl alcohols (Achmatowicz reaction) and furfuryl amines (aza-Achmatowicz reaction) provide access to highly functionalized heterocyclic structures that have been employed as intermediates in synthetic routes for the preparation of complex molecules including carbohydrates and alkaloids. Complete oxidative degradation of the furan ring affords carboxylic acids; thus the oxygen heterocycle has served as a masked carboxyl group in many synthetic studies. These transformations and their applications in total syntheses are covered in this chapter. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Furan; \u0000Oxidation; \u00001,4-Dicarbonyl Compounds; \u00004-Oxoalkenals; \u00004-Oxoalkenoic Acids; \u0000Carboxylic Acids; \u0000Ozone; \u0000Singlet Oxygen; \u0000Ruthenium Tetroxide; \u0000Singlet oxygen; \u00004-Hydroxybutenolides; \u0000Achmatowicz Reaction; \u0000Hydrogen Peroxide; \u0000N-Bromosuccinimide; \u0000tert-Butylhydroperoxide; \u0000meta-Chloroperbenzoic Acid; \u0000Magnesium Monoperoxyphthalate","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"73 1","pages":"1-256"},"PeriodicalIF":0.0,"publicationDate":"2015-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85449733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}