Organic ReactionsPub Date : 2011-12-16DOI: 10.1002/0471264180.OR075.01
T. RajanBabu
{"title":"Hydrocyanation of Alkenes and Alkynes","authors":"T. RajanBabu","doi":"10.1002/0471264180.OR075.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR075.01","url":null,"abstract":"Hydrogen cyanide is an abundantly available feedstock that is useful for the synthesis of organonitrile intermediates, which serve as precursors for amines, amides, isocyanates, carboxylic acid, and esters. Many of these compounds are used in the manufacture of polymers, agrichemicals, cosmetics, and pharmaceuticals. Hydrogen cyanide itself is relatively unreactive, but in the presence of a catalyst HCN adds to carbonyl compounds, alkenes, and alkynes offering a direct and economical way to such organonitrile intermediates. This chapter focuses primarily on the metal-catalyzed hydrocyanation of alkenes or alkynes. Acetone cyanohydrin and trimethylsilyl cyanide (TMSCN), both commercially available reagents, can be used for the in-situ generation of HCN. In some transition-metal catalyzed additions, TMSCN acts as a surrogate for HCN, giving products where the TMS group replaces the hydrogen. Preparatively, these reagents provide some advantages since the handling of toxic HCN is avoided. Reactions of these reagents are included here under appropriate substrate and direct comparison of yield and selectivity can be made. Keywords: Hydrocyanation; Alkenes; Alkynes; Asymmetric hydrocyanation; Metal catalysts; Norbornene; Vinylarenes; 1,3-Dienes; Safety; Hydrogen cyanide; Conjugate addition; Mechanisms; Experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"75 1","pages":"1-74"},"PeriodicalIF":0.0,"publicationDate":"2011-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79251494","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}
Organic ReactionsPub Date : 2011-12-16DOI: 10.1002/0471264180.OR075.03
Wen-Tau T. Chang, Russell C. Smith, Christopher S. Regens, A. Bailey, N. Werner, S. Denmark
{"title":"Cross‐Coupling with Organosilicon Compounds","authors":"Wen-Tau T. Chang, Russell C. Smith, Christopher S. Regens, A. Bailey, N. Werner, S. Denmark","doi":"10.1002/0471264180.OR075.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR075.03","url":null,"abstract":"Organosilicon functions possess many properties that make them ideal donors of organic groups in cross-coupling reactions. Through the addition of an appropriate silicophilic Lewis base, an in situ pentacoordinate silane can effectively transfer an organic group. This feature allows for the rapid development of silicon cross-coupling methods that continue today. Organosilicon-based cross-coupling has now become a practical, viable, and in some cases, superior compared with organoboron,-zinc,-tin couplings. The unique properties of organosilicon compounds provide a number of distinct advantages to their use as donors in transition-metal catalyzed cross-coupling reactions: 1, silicon moieties can be introduced into organic substrates by many general and high-yielding methods for the construction of silicon carbon bonds; 2, organosilicon reagents are chemically robust and allow isolation and purification of products and are compatible with many functional groups; 3, silicon-containing by-products of the coupling are of low molecular weight, are nontoxic, and are easily removed from the reaction mixture; 4, a number of mild methods are available. \u0000 \u0000 \u0000 \u0000This chapter presents a thorough overview of the various combinations of transferable groups and organic electrophiles. The scope is limited to the combination of silicon-bearing nucleophiles with halo or related electrophiles under catalysis by palladium or nickel complexes wherein the silyl halide is lost. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Cross coupling; \u0000Organosilicon compounds; \u0000Alkenylsilanes; \u0000Allylsilanes; \u0000Benzylsilanes; \u0000Halosilanes; \u0000Silanols; \u0000Silanolates; \u0000Alkoxysilanes; \u0000Polysiloxanes; \u0000Disiloxanes; \u0000Cyclic silyl ethers; \u0000Ruthenium catalysts; \u0000Palladium; \u0000Ligands; \u0000Solvents; \u0000Fluoride; \u0000Mechanisms; \u0000Enantioselectivity; \u0000Experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"22 1","pages":"213-746"},"PeriodicalIF":0.0,"publicationDate":"2011-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82442689","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR003.04
C. Suter, A. W. Weston
{"title":"Direct Sulfonation of Aromatic Hydrocarbons and their Halogen Derivatives","authors":"C. Suter, A. W. Weston","doi":"10.1002/0471264180.OR003.04","DOIUrl":"https://doi.org/10.1002/0471264180.OR003.04","url":null,"abstract":"This chapter deals with the direct replacement of the hydrogen atoms in aromatic hydrocarbons, and their halogen derivatives by sulfonic acid, sulfonyl chloride, and sulfonyl fluoride groups. These sulfonations are more convenient and much more commonly used than indirect synthetic methods such as those that involve the reaction of an aryl halide with a sulfite, the oxidation of a disulfide, thiol, or sulfinic acid, or the conversion of a diazonium salt into a sulfonic acid. The reagents most used for direct sulfonation are sulfuric acid, sulfur trioxide in an inert solvent, in sulfuric as oleum, or an addition product with pyridine or dioxane, Chlorosulfonic acid, its salts and its anhydride and flurosulfonic acid. Combinations of reagents have been used. \u0000 \u0000 \u0000Keywords: \u0000 \u0000direct sulfonation; \u0000aromatic hydrocarbons; \u0000halogen derivatives; \u0000sulfuric acid; \u0000sulfur trioxide; \u0000side reactions; \u0000applications; \u0000sulfonic acids; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"20 1","pages":"141-197"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74241521","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR017.01
D. Bublitz, K. Rinehart
{"title":"The Synthesis of Substituted Ferrocenes and other π‐Cyclopentadienyl‐Transition Metal Compounds","authors":"D. Bublitz, K. Rinehart","doi":"10.1002/0471264180.OR017.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR017.01","url":null,"abstract":"The discovery of dicyclopentadienyliron (ferrocene) in 1951 led to the development of an entirely new area of organometallic chemistry that of the pi-metallohydrocarbons. Representative compounds are the pi-metalloarenes such as dibenzenechromium, the pi-methallopseudoarenes such as ferrocene, and the pi-metalloolefin complexes such as butadiene iron tricarbonyl Since there is a great amount of literature available at this time, the treatment here is limited to three dimensions: to include only compounds containing cyclopentadienyl rings, of these to include only those which have shown to undergo aromatic substitution,reactions and within this group only synthetic aspects of their chemistry. This nearly restricts the discussion to syntheses of substituted ferrocenes. \u0000 \u0000 \u0000Keywords: \u0000 \u0000substituted ferrocenes; \u0000pi-cyclopentadienyl-transition metal compounds; \u0000intermediates; \u0000cyclopentadienes; \u0000ruthenocene; \u0000osmocene; \u0000cyclopentadienylmanganese tricarbonyl. metal cyclopenatdienyl carbonyls; \u0000nitrosyl dicarbonyls; \u0000syntheses; \u0000ferrocene; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"60 1","pages":"1-154"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74838099","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR007.03
J. Brewster, E. Eliel
{"title":"Carbon-Carbon Alkylations with Amines and Ammonium Salts","authors":"J. Brewster, E. Eliel","doi":"10.1002/0471264180.OR007.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR007.03","url":null,"abstract":"This chapter is a review of those reactions of compounds containing labile amino groups in which a carbon-carbon bond is formed by amine replacement as, for example, in the alkylation of diethyl malonate by 1-dimethylamino-3-butanone. Attention has been given primarily to reactions of amines prepared by the Mannich reaction (Mannich bases), but for comparison, analogous reactions of simpler quaternary ammonium salts have been included. \u0000 \u0000 \u0000Keywords: \u0000 \u0000carbon-carbon alkylations; \u0000amines; \u0000ammonium salts; \u0000cyanide; \u0000replacements; \u0000active methyl groups; \u0000active methylene groups; \u0000indole; \u0000quaternary salts; \u0000organometallic compounds; \u0000related reactions; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"916 1","pages":"99-197"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77530125","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR022.01
S. Rhoads, N. R. Raulins
{"title":"The Claisen and Cope Rearrangements","authors":"S. Rhoads, N. R. Raulins","doi":"10.1002/0471264180.OR022.01","DOIUrl":"https://doi.org/10.1002/0471264180.OR022.01","url":null,"abstract":"Since the first observation of a thermal rearrangement vinyl allyl ether to the corresponding homoallylcyclic carbonyl compound by Claisen in 1912, rearrangements of vinyl and aryl allylic ethers have been extensively studied and exploited for their synthetic value. The corresponding rearrangement of substituted 1,5-hexadiene was first recognized by Cope in 1940 as the carbon analog of the Claisen rearrangement. Today it is recognized that such transformations fall within the general category of a [3,3] sigamtropic reaction and that considerable variation may be accommodated in the basic requirement of a system of six atoms with terminal unsaturated linkage. This chapter attempts to survey the vas t accumulation of Claisen and Cope rearrangements recorded since the first coverage in 1944. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Claisen rearrangments; \u0000Cope rearrangements; \u0000allyl ethers; \u0000aliphatic rearrangements; \u0000anomalies; \u0000amine rearrangements; \u0000thio rearrangements; \u0000migration; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"14 1","pages":"1-252"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85017828","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR019.03
J. Mcomie, J. Blatchly
{"title":"The Thiele‐Winter Acetoxylation of Quinones","authors":"J. Mcomie, J. Blatchly","doi":"10.1002/0471264180.OR019.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR019.03","url":null,"abstract":"In 1898, Johannes Thiele described the reaction of p-benzoquinone with acetic acid in the presence of a small quantity of sulfuric acid to give 1,2,4-triacetoxybenzene in 80% yield. Later Thiele and Winter described further experiments that showed both 1,2- and 1,4-naphthoquinone gave 1,2,4-triacetoxynaphthalene and that the same product was obtained when sulfuric acid was replaced by zinc chloride. Thiele-Winter acetoxylation can be defined as the acid-catalyzed reactions of quinones with acetic acid to give triacetoxy aromatic compounds. This reaction has been carried out on a large number of quinones and to this point there has been no review. Very little work has been done on the reaction of quinones with anhydrides other than acetic anhydride. Results of these studies are summarized. Reactions with other anhydrides are discussed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Thiele-Winter acetoxylation; \u0000quinones; \u0000benzoquinones; \u0000naphthoquinones; \u0000anhydride; \u0000triacetates; \u0000butylquinones; \u0000methylquinones; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"60 1","pages":"199-277"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85480996","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR022.03
E. Vedejs
{"title":"Clemmensen Reduction of Ketones in Anhydrous Organic Solvents","authors":"E. Vedejs","doi":"10.1002/0471264180.OR022.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR022.03","url":null,"abstract":"The Clemmensen reduction of ketones and aldehydes using zinc and hydrochloric acid is the simplest direct method for converting the carbonyl group into a methylene group. Typically the carbonyl is refluxed for several hours with 40% hydrochloric acid, amalgamated zinc, and a water-immiscible organic solvent such as tolurene. Because of these harsh conditions, reports of successful Clemmensen reduction of polyfunctional ketones have been rare. A milder procedure using dry hydrogen chloride in organic solvent extends the potential of this reaction. Other developments that define scope of both aqueous and anhydrous reduction conditions are discussed and an effort is made to compare the properties of possible reduction intermediates with other organozinc species. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Clemmensen reduction; \u0000ketones; \u0000anhydrous organic solvents; \u0000diketones; \u0000unsaturated ketones; \u0000hindered ketones; \u0000activated zinc dust; \u0000cholestane; \u00001,1-diphenylclohexane; \u00004,4-dideuterio-1,1-diphenylcyclohexane; \u0000hydrogen chloride; \u0000aprotic organic solvents; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"1 1","pages":"401-422"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78592107","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR002.03
T. A. Geissman
{"title":"The Cannizzaro Reaction","authors":"T. A. Geissman","doi":"10.1002/0471264180.OR002.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR002.03","url":null,"abstract":"The reaction in which two aldehyde groups are transformed into the corresponding hydroxyl and carbonyl functions, existing separately or in combination as an ester, has been termed the Cannizzaro reaction. Here the discussion is restricted to the dismutation of two similar aldehyde groups into the corresponding alcohol and carboxylic salt function by means of aqueous or alcoholic and alkali. The conversion of benzaldehyde into a mixture of benzyl alcohol and sodium benzoate is an example. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Cannizzaro reaction; \u0000aliphatic aldehydes; \u0000aromatic aldheydes; \u0000heterocyclic aldehydes; \u0000crossed Cannizzaro reaction; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"92 1","pages":"94-113"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82288320","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}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR011.03
C. Rondestvedt
{"title":"Arylation of Unsaturated Compounds by Diazonium Salts (The Meerwein Arylation Reaction)","authors":"C. Rondestvedt","doi":"10.1002/0471264180.OR011.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR011.03","url":null,"abstract":"The arylation of olefinic compounds by diazonium halides with a copper salt catalyst was discovered by Meerwein. The Meerwein arylation reaction proceeds best when the olefinic double bond is activated by an electron attracting group Z, such as cyano, carbonyl, or aryl. The net result is the union of the aryl group from diazonium salt with carbon atom beta to the activating group, either by substitution of a beta hydrogen atom or the addition of Ar and Cl to the double bond. The reaction is a valuable synthetic tool. This chapter is confined to reactions in which a new carbon-carbon bond is formed between the aromatic ring of a diazonium salt and aliphatic unsaturated compound. \u0000 \u0000 \u0000Keywords: \u0000 \u0000arylation; \u0000unsaturated compounds; \u0000diazonium salts; \u0000Meerwein arylation reaction; \u0000unsaturated component; \u0000quinones; \u0000arylation; \u0000cinnamic acid; \u0000maleic acid; \u0000side reactions; \u0000decarboxylation; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"74 1 1","pages":"189-260"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86915226","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}
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