Application of Inorganic Reagents in Organic name Reactions
Navjeet Kaur*, Neha Garg and Dharma Kishore
Department of Chemistry, Banasthali University, Banasthali-304022 (Rajasthan), India
*Corresponding Author E-mail:nvjithaans@gmail.com
ABSTRACT:
Chemical reagents bring about various types of changes in organic molecules to yield products of immense value. A few of the most important and widely used inorganic metals, non-metals and reagents based on them in organic name reactions have been discussed in this review
KEYWORDS: Organic name reactions, Rearrangements, Inorganic reagents, Condensation, Coupling.
1. INTRODUCTION:
There are a large number of organic reactions and molecular rearrangements which are of wide synthetic importance and applications and hence associated with the names of their discoverers. Organic reactions involve reagents and substrates. A group of compounds serve as substrates for a particular type of reaction when treated with a specific reagent.
A reagent is a "substance or compound that is added to a system in order to bring about a chemical reaction". In organic chemistry, reagents are compounds or mixtures, usually composed of inorganic or small organic molecules that are used to affect a transformation on an organic substrate. Examples of organic reagents include the Collins reagent, Fenton's reagent, and Grignard reagent. There are also analytical reagents which are used to confirm the presence of another substance. Examples of these are Fehling's reagent, Millon's reagent and Tollens' reagent.
Nowadays a plenty of reagents for modern organic synthesis are available to the organic chemist to choose among and carry out the reaction smoothly to the desired product on both laboratory and industrial scales. The purpose of this review is to highlight some of the applications of inorganic reagents in organic name reactions.
Inorganic chemicals are substances of mineral origin that do not contain carbon in their molecular structure with the exception of carbon oxides and carbon disulphide or the compounds containing one or more metal atoms are considered to be inorganic.
Transition metal-catalyzed cross-coupling reactions of organometallic reagents with organic electrophiles represent one of the most powerful methods for the construction of carbon-carbon bonds. The application of a variety of inorganic oxidizing agents to organic substrates has broadened considerably the selectivity with which such oxidations may be carried out. The availability of a wide range of complex hydride reducing agents has greatly simplified the problem of selective reduction of functional groups. The technique of catalytic hydrogenation can be applied almost universally to the unsaturated systems, and therein lie its chief advantage. The classical methods for the addition of halogen to double bonds or the substitution of halogen for hydroxyl by hydrohalic acids are too well known. The rearrangement of certain saturated hydrocarbons under the influence of Lewis acids has been known for some time. Mercury (II) salts are sufficiently electrophilic to activate alkenes towards nucleophilic attack. Organozinc reagents are used extensively in organic synthesis to find useful pathways to organic products.
The some of those organic name reactions are given below:
Acyloin Condensation: When carboxylic acid esters are refluxed with metallic sodium in aprotic solvents α-hydroxy ketones called acyloins are formed.1
Appel Reaction: The reaction of triphenylphosphine and tetrahalomethanes with alcohols convert an alcohol to the corresponding alkyl halide.2
Arens-Van Dorp Synthesis: The reaction involves preparation of alkoxyethynyl alcohols from ketones and ethoxyacetylene in presence of alkali metal amide.3
Arndt-Eistert Synthesis: The reaction consists in increasing the length of the carbon chain by one methylene group in carboxylic acids.4
Baeyer-Villiger Oxidation: The reaction involves the oxidation of ketones to esters, is carried out with peracids or with hydrogen peroxide and a Lewis acid.5
Balz-Schiemann Reaction: The aryl amines get converted to aryl fluorides via diazotisation followed by thermal decomposition of the derived tetrafluoroborates.6
Bart Reaction: Formation of aromatic arsonic acids by treating aromatic diazonium compounds with alkali arsenites in the presence of cupric salts or powdered silver or copper.7
Barton Deoxygenation: Deoxygenation of thiocarbonyl derivatives of alcohols upon treatment with tri-n-butyltin hydride.8
Barton Olefin Synthesis: Olefin synthesis by extrusion of nitrogen and sulfur from 1,3,4-thiadiazoline intermediate.9
Bechamp Reduction: Reduction of aromatic nitro compounds to the corresponding amines by iron, ferrous salts or iron catalysts in aqueous acid.10
Beckmann Rearrangement: The acid-catalysed conversion of ketoximes to amides is known as Beckmann Rearrangement.11
Benary Reaction: Action of Grignard reagents on enamino ketones to yield β-substituted α,β-unsaturated ketones.12
Benkeser Reduction: Reduction of aromatic and olefinic compounds with lithium or calcium to monounsaturated olefins, as well as the fully reduced products.13
Benzidine rearrangement: Boron trifluoride brings about the Benzidine rearrangement.14
Benzoin Condensation: Cyanide-catalyzed condensation of aromatic aldehydes to give benzoins.15
Bernthsen Acridine Synthesis: Formation of 5-substituted acridines by heating diarylamines in organic acids or anhydrides in the presence of zinc chloride.16
Birch Reduction: When aromatic rings are reduced with sodium, potassium or lithium in lquid ammonia in presence of alcohol addition of hydrogen takes place at 1 and 4 positions to give an unconjugated diene.17
Bischler-Napieralski Reaction: Cyclodehydration of β-phenethylamides to 3,4-dihydroisoquinoline derivatives in the presence of zinc chloride.18
Blaise Ketone Synthesis: Formation of ketones by treatment of acid halides with organozinc compounds.19
Blaise Reaction: This reaction involves the formation of β-oxoesters by treatment of α-bromocarboxylic esters with zinc in the presence of nitriles. The intermediate organozinc compound reacts with the nitrile and the complex is hydrolyzed with 30% potassium hydroxide.20
Blanc Reaction: The reaction is useful for the preparation of chloromethylated arenes from the parent arene with formaldehyde, HCl and ZnCl2.21
Bodroux-Chichibabin Aldehyde Synthesis: Formation of aldehydes by treatment of orthoformates with Grignard reagents. 22(a,b)
Bodroux Reaction: Formation of substituted amides by reaction of a simple aliphatic or aromatic ester with an aminomagnesium halide.23
Bohn-Schmidt Reaction: Hydroxylation of anthraquinones containing at least one hydroxyl group by treatment with sulfuric acid and boric acid in the presence of a catalyst such as mercury.24
Boord Olefin Synthesis: Regiospecific synthesis of olefins from aldehydes and Grignard reagents by zinc induced reductive elimination of halogen and alkoxy groups.25
Borsche-Drechsel Cyclization: Formation of carbazole by acid-catalyzed rearrangement of cyclohexanone phenylhydrazone to tetrahydrocarbazole followed by oxidation.26
Bouveault Aldehyde Synthesis: Action of Grignard reagent on N,N-disubstituted formamides yields the homologous aldehydes.27
Bouveault-Blanc Reduction: Alcohols are formed from aldehydes, ketones and esters on treatment with excess of sodium and alcohol.28
Brown Hydroboration: The syn-addition of hydroboranes to alkenes occurs, boron add to the least hindered carbon.29
Bucherer-Bergs Reaction: The reaction of ketone with potassium cyanide and ammonium carbonate leads to the formation of hydantoins.30
Bucherer Carbazole Synthesis: Formation of carbazoles from naphthols aryl hydrazines and sodium bisulfate.31
Buchwald-Hartwig Cross Coupling Reaction: The reaction involves palladium-catalyzed synthesis of aryl amines from aryl halides and primary or secondary amines.32
Cadiot-Chodkiewicz Coupling: The Cu+ catalyzed coupling of a terminal alkyne and an alkynyl halide to unsymmetrical bisacetylenes.33
Castro-Stephens Coupling: The coupling of cuprous acetylides with aryl halides to yield arylacetylenes.34
Chan-Lam Coupling: This reaction allows aryl carbon-heteroatom bond formation via an oxidative coupling of arylboronic acids, with amines by Cu2+. 35
Chichibabin Reaction: Pyridine in toluene on treatment with sodamide at 100oC-200oC gives 2-aminopyridine i.e. amination of pyridine.36
Claisen sigmatropic rearrangement: Tebbe methylenation of the chloro-difluorovinyl-substituted lactone shown in equation affording the corresponding ring expanded product upon heating at 85° C.37
Clemmensen Reduction: The reduction of carbonyl groups of aldehydes and ketones to methylene groups with amalgamated zinc and concentrated hydrochloric acid is known as Clemmensen Reduction.38
Corey-Bakshi-Shibata Reduction: This is the reduction of ketones by borane and a chiral oxazaborolidine as catalyst.39
Corey-Fuchs Reaction: This reaction allows the preparation of terminal alkynes by one-carbon homologation of an aldehyde. The first step leads to a dibromoalkene followed by treatment with a lithium base generates the terminal alkyne.40
Criegee Reaction: Oxidative cleavage of vicinal glycols by lead tetraacetate.41
Darzens-Nenitzescu Synthesis of Ketones: Acylation of olefins with acid chlorides catalyzed by Lewis acids.42
Dess-Martin Oxidation: Mild oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, employing the triacetoxyperiodinane.43
Diazotisation: The nitrosation of primary aromatic amines with nitrous acid (generated in situ from sodium nitrite and a strong acid) leads to diazonium salts.44
Doering-LaFlamme Allene Synthesis: Treatment of an olefin with bromoform and an alkoxide to yield the 1,1-dibromocyclopropane which reacts with an active metal to produce an allene.45
Dowd-Beckwith Ring Expansion Reaction: Free radical mediated ring expansions of haloalkyl β-ketoesters.46
Eglinton Reaction: The Eglinton Reaction is the synthesis of symmetric or cyclic bisacetylenes via reaction of the terminal alkyne in presence of copper (II) salt in pyridine by an oxidative coupling of terminal alkynes.47
Emde Degradation: This is a method for reductive cleavage of the carbon-nitrogen bond by treatment of an alcoholic or aqueous solution of a quaternary ammonium halide with sodium amalgam.48
Emmert Reaction: Formation of pyridyldialkylcarbinols by condensation of ketones with pyridine in the presence of aluminum or magnesium amalgam.49
Ene Reaction: Ene Reaction is a reaction of a double bond with an allylic system when an allylic hydrogen and the olefinic terminus of the allylic system add across the double bond.50
Etard Reaction: Oxidation of an arylmethyl group to an aldehyde by treatment with chromyl chloride.51
Ferrier Rearrangement: The conversion of hex-5-enopyranosides into cyclohexanones catalyzed by mercury (II) salts.52
Finkelstein Reaction: Treatment of a primary alkyl halide with an alkali metal halide leads to replacement of the halogen.53
Fischer Esterification: The Lewis acid catalyzed esterification of carboxylic acids with alcohols to give esters.54
Fischer Indole Synthesis: The conversion of aryl hydrazones to indoles requires the addition of Lewis acids.55
Fischer Phenylhydrazine Synthesis: Formation of arylhydrazines by reduction of diazo compounds with excess sodium sulfite and hydrolysis of the substituted hydrazine sulfonic acid salt with hydrochloric acid.56
Frankland-Duppa Reaction: Formation of α-hydroxycarboxylic esters by reaction of dialkyl oxalates with alkyl halides in the presence of zinc.57
Frankland Synthesis: Synthesis of zinc dialkyls from alkyl halides and zinc.58
Friedel-Crafts Reaction: Alkylation and acylation of the aromatic compounds with alkyl halides and acid halides in presence of Lewis acid catalyst, is known as Friedel-Crafts Reaction.59
Fries Rearrangement: Phenolic ethers on heating with aluminium trichloride give o- and p-acylphenol.60
Fujimoto-Belleau Reaction: Synthesis of cyclic α-substituted α,β-unsaturated ketones from enol lactones and Grignard reagents.61
Fukuyama Coupling: The palladium catalyzed coupling of organozinc compounds with thioesters to form ketones.62
Gattermann Aldehyde Synthesis: A mixture of carbon monoxide and hydrochloric acid is passed through a solution of benzene containing anhydrous aluminium chloride and cuprous chloride.63
Gattermann-Koch Reaction: Formylation of benzene with carbon monoxide and hydrogen chloride in the presence of aluminum chloride and cuprous chloride.64
Glaser Coupling: The Glaser Coupling is a synthesis of symmetric or cyclic bisacetylenes via a coupling reaction of terminal alkynes by the use of catalytic copper (I).65
Gomberg Free Radical Reaction: Formation of free radicals by abstraction of the halogen from triarylmethyl halides with metals.66
Grignard Degradation: Stepwise dehalogenation of a polyhalo compound through its Grignard reagent which on treatment with water yields a product containing one halogen atom less.67
Grignard Reaction: It is the addition of Grignard reagents to carbonyl compounds to generate alcohols.68
Grundmann Aldehyde Synthesis: Transformation of an acid into an aldehyde of the same chain length by conversion of the acid chloride, via the diazo ketone, to the acetoxy ketone, reduction with aluminum isopropoxide and hydrolysis to the glycol, and cleavage with lead tetraacetete.69
Haller-Bauer reaction: Ketones are cleaved to give amides with sodamide, which subsequently gives acids on reaction with nitrous acid.70
Haloform Reaction: The reaction involves the formation of haloform on the reaction of carboxylic acid with corresponding halogen in presence of alkali.71
Hantzsch Dihydropyridine Synthesis: This reaction allows the preparation of dihydropyridine derivatives by condensation of an aldehyde with two equivalents of a β-ketoester in the presence of ammonia.72
Haworth Phenanthrene Synthesis: Preparation of phenanthrenes from naphthalenes including Friedel-Crafts acylation and Clemmensen reductions.73
Hay Coupling: The copper-TMEDA complex used is soluble in a wider range of solvents, so that the reaction is more versatile than Glaser Coupling.74
Heck Reaction: The palladium-catalyzed C-C coupling between aryl halides and activated alkenes in the presence of a base is called as the Heck Reaction.75
Helferich Method: Glycosidation of an acetylated sugar by heating with a phenol in the presence of ZnCl2.76
Hell-Volhard-Zelinsky Reaction: Aliphatic carboxylic acids react with bromine or chlorine in presence of small amount of red phosphorus to give exclusively mono-α-halogenated acids. 77(a-c)
Henkel Reaction: Rearrangement of alkaline salts of aromatic acids to symmetrical diacids in the presence of cadmium or other metallic salts.78
Hiyama Coupling: It is the palladium-catalyzed C-C bond formation between aryl, alkenyl or alkyl halides or pseudohalides and organosilanes.79
Hoch-Campbel Az iridine Synthesis: Formation of aziridines by treatment of ketoximes with Grignard reagents and subsequent hydrolysis of the organometallic complex.80
Hofmann Elimination: This elimination reaction is suitable for producing alkenes with one or two substituents.81
Hooker Reaction: Oxidation of 2-hydroxy-3-alkyl-1,4-quinones with dilute alkaline permanganate with shortening of the alkyl side chain by a methylene group and simultaneous exchange of hydroxyl and alkyl group positions.82
Hosomi-Sakurai Reaction: The Hosomi Sakurai Reaction involves the Lewis acid-promoted allylation of various electrophiles with allyltrimethysilane.83
Houben-Hoesch Reaction: Polyhydroxy phenols and some reactive heterocyclic compounds undergo acylation with nitrile and hydrochloric acid in the presence of lewis acid. 84(a,b)
Hunsdiecker Reaction: This reaction involves the bromodecarboxylation of silver salt of a carboxylic acid.85
Ireland-Claisen Rearrangement: This Rearrangement employs the allyl ester of a carboxylic acid and is converted to its silyl-stabilized enolate which rearranges at temperatures below 100 °C.86
Jones Oxidation: The oxidation of primary and secondary alcohols to acids and ketones, respectively, in the presence of chromic acid, aqueous sulfuric acid and acetone.87
Jourdan-Ullmann-Goldberg Synthesis: Synthesis of substituted diphenylamines in presence of copper powder. 88(a,b)
Julia Olefination: This multistep synthesis enables the preparation of (E)-alkenes. The addition of a phenylsulfonyl carbanion to an aldehyde or ketone leads to an intermediate alcohol followed by the reductive elimination with sodium amalgam to furnish the alkene.89
Knoop-Oesterlin Amino Acid Synthesis: Preparation of α-amino acids by catalytic hydrogenation of α-oxo acids in aqueous ammonia in the presence of platinum, palladium or Raney nickel catalysts.90
Kochi Reaction: The Kochi Reaction is a one-carbon oxidative degradation of carboxylic acids by using Pb (IV) reagent as the oxidant.91
Koenigs-Knorr Synthesis: Formation of glycosides from acetylated glycosyl halides and alcohols or phenols in the presence of silver salts.92
.
Krafft Degradation: Conversion of carboxylic acids into the next lower homologue by dry distillation of the alkaline earth salt with the corresponding acetate which is followed by chromic acid oxidation.93
Kucherov Reaction: Hydration of acetylenic hydrocarbons with dilute sulfuric acid in the presence of mercuric sulfate as catalyst.94
Kuhn-Winterstein Reaction: Conversion of 1,2-glycols into trans olefins by reaction with diphosphotetraiodide.95
Kumada Coupling: The coupling of Grignard reagents with alkyl, vinyl or aryl halides under Ni-catalysis provides hydrocarbons.96
Lossen Rearrangement: It involves the conversion of a hydroxamic acid to an isocyanate in presence of tosyl chloride. In the presence of amines, ureas are formed; in the presence of water, amines containing one less carbon than the starting material are generated.97
Luche Reduction: This is the selective 1,2-reduction of enones with sodium borohydride with CeCl3.98
Malaprade Reaction: Compounds containing two hydroxyl groups attached to adjacent carbon atoms undergo cleavage of the carbon-carbon bond when treated with periodic acid to yield aldehydes.99
McMurry Reaction: The coupling is induced by single electron transfer to the carbonyl groups from alkali metal and in second step deoxygenation of the 1,2-diol with low-valent titanium to yield the alkene.100
Meerwein Arylation: Formation of arylated olefins on treatment of olefins with diazonium salts in the presence of cupric salts.101
Meerwein-Ponndorf-Verley Reduction: The reaction involves the reduction of aldehydes and ketones to alcohols by treatment with aluminium isopropoxide in excess of isopropyl alcohol. 102(a,b)
Miescher Degradation: Conversion of the methyl ester of the bile acid to the tertiary alcohol, followed by dehydration, bromination, dehydrohalogenation and oxidation of the diene yields the chain-shortened ketone.103
Mignonac Reaction: Formation of amines by catalytic hydrogenation of aldehydes or ketones in liquid ammonia and absolute ethanol in the presence of a nickel catalyst.104
Milas Hydroxylation of Olefins: Formation of cis-glycols by reaction of alkenes with hydrogen peroxide and either ultraviolet light or a catalytic amount of osmium, vanadium, or chromium oxide.105
Mitsunobu Reaction: The Mitsunobu Reaction allows the conversion of primary and secondary alcohols to esters and various other compounds in presence of suitable nitrogen nucleophiles include hydrogen azide followed by subsequent hydrolysis or selective reduction to the corresponding amines.106
Miyaura Borylation Reaction: The Miyaura borylation reaction enables the synthesis of boronates by cross-coupling of bis(pinacolato)diboron (B2pin2) with aryl halides and vinyl halides.107
Modified Julia-Kociensky Olefination: The Modified Julia Olefination enables the preparation of alkenes from benzothiazol-2-yl sulfones and aldehydes in a single step.108
Mukaiyama Aldol Addition: The trimethylsilyl group is thought of as a sterically demanding hydrogen equivalent that activates the enol and traps the aldol hydroxyl.109
Mukaiyama-Michael Reaction: Formation of 1,5-dicarbonyl compounds by reaction of ketene silyl acetals with α,β-unsaturated ketones and esters.110
Nagata Hydrocyanation: Alkylaluminum-mediated 1,4-addition of hydrogen cyanide to α,β-unsaturated carbonyl compounds.111
Nametkin isomerization: This isomerization is the acidic hydrolysis of borneol-type substance to give camphene-like structures, the W-M rearrangement.112
Nazarov Cyclization Reaction: Protic or Lewis acid-catalyzed electrocyclic ring closure of divinyl ketones to yield 2-cyclopentenones.113
Negishi Coupling: The Negishi Coupling, published in 1977, allowed the preparation of unsymmetrical biaryls in good yields. The versatile nickel or palladium catalyzed coupling of organozinc compounds with various halides.114
Nenitzescu Reductive Acylation: Hydrogenative acylation of cycloolefins with acid chlorides in the presence of aluminum chloride.115
Nozaki-Hiyama Coupling Reaction: This coupling between halides and aldehydes is a chromium-induced redox reaction.116
Oppenauer Oxidation: The reaction involves the oxidation of a secondary alcohol with a ketone and a base to the corresponding ketone of the alcohol.117
Overman Rearrangement: Formal [3,3]-sigmatropic rearrangement of the trichloroacetimidate of allylic alcohols to allylic trichloroacetamides.118
Pauson-Khand Reaction: The Pauson-Khand Reaction is a [2+2+1] cycloaddition of an alkyne, an alkene and carbon monoxide.119
Pechmann Condensation Coumarin Synthesis: The Pechmann Condensation allows the synthesis of coumarins by reaction of phenols with β-keto esters with a strong Lewis acid such as AlCl3.120
Perkow Reaction: Formation of enol phosphates on treatment of α-halocarbonyl compounds with trialkyl phosphites.121
Peterson Olefination: The Peterson Reaction allows the preparation of alkenes from α-silylcarbanions.122
Pictet-Gams Isoquinoline Synthesis: Formation of isoquinolines by cyclization of acylated aminomethyl phenyl carbinols with phosphorus pentoxide in toluene or xylene.123
Pictet-Hubert Reaction: Phenanthridine cyclization by dehydrative ring closure of acyl-o-aminobiphenyls on heating with zinc chloride at 250-300°.124
Pinacol Coupling Reaction: This reaction involves the reductive homo-coupling of a carbonyl compound to produce a symmetrically substituted 1,2-diol.125
Pinner Reaction: The Pinner Reaction is the partial solvolysis of a nitrile to yield an iminoether. Treatment of the nitrile with gaseous HCl in a mixture of anhydrous chloroform and an alcohol produces the imino ether hydrochloride.126
Pinner Triazine Synthesis: Preparation of 2-hydroxy-4,6-diaryl-s-triazines by reaction of aryl amidines and phosgene. The reaction may be extended to halogenated aliphatic amidines.127
Ponzio Reaction: Formation of dinitrophenylmethanes from benzaldoximes by oxidation with nitrogen dioxide in ether.128
Prevost Reaction: Hydroxylation of olefins with iodine and silver benzoate in an anhydrous solvent to give trans-glycols.129
Pschorr Reaction: This reaction allows the preparation of biaryl tricyclics by intramolecular substitution of one arene by an aryl radical in presence of a radical that is generated in situ from an aryl diazonium salt by copper catalysis.130
Purdie Methylation: Exhaustive methylation of a methyl glycoside by repeated treatment with methyl iodide and silver oxide, followed by hydrolysis of the pentamethyl ether with dilute acid to yield the anomeric hydroxyl group.131
Quelet Reaction: Passage of dry hydrochloric acid through a solution of phenolic ether and an aliphatic aldehyde in the presence of a dehydration catalyst to yield α-chloroalkyl derivatives.132
Raschig Phenol Process: Commercial process for the production of phenol by the hydrolysis of chlorobenzene, produced by the chlorination of benzene with hydrochloric acid and air.133
Reformatsky Reaction: Preparation of β-hydroxyesters by the treatment of a reactive organic halide with a carbonyl compound in the presence of a zinc metal and subsequent hydrolysis.134
Reisert Indole Synthesis: Condensation of an o-nitrotoluene with oxalic ester, reduction to the amine, and cyclization to the indole.135
Riehm Quinoline Synthesis: Formation of quinoline derivatives by prolonged heating of arylamine hydrochlorides with ketones with use of aluminum chloride or phosphorus pentachloride.136
Riley Oxidations: Oxidations of organic compounds with selenium dioxide.137
Rosenmund Reduction: The catalytic hydrogenation of acid chlorides allows the formaion of aldehydes. The Pd catalyst must be poisoned, with BaSO4 because the untreated catalyst will give some overreduction.138
Rosenmund-von Braun Synthesis: Conversion of aryl halides to aromatic nitriles in the presence of cuprous cyanide.139
Ruf-Fenton Degradation: Shortening of the carbon chain of sugars by the oxidation of aldonic acids with hydrogen peroxide and ferric salts. 140(a, b)
Saegusa Oxidation: Conversion of silyl enol ethers into corresponding α,β-eneones using stoichiometric amounts of palladium acetate.141
Sandmeyer Reaction: Sandmeyer Reaction affords a useful method for introducing a halogen substituent at the desired position of an aromatic ring.142
Sandmeyer Diphenylurea Isatin Synthesis: Formation of a cyanoformamidine by treatment of a symmetrical diphenylthiourea with potassium cyanide in alcohol containing lead carbonate, ring-closure with aluminum chloride in benzene or carbon disulfide to isatin.143
Sarett Oxidation: Oxidation of primary and secondary alcohols to aldehydes and ketones by means of CrO3-pyridine complex.144
Schmidt Reaction: Carboxylic acids and hydrazoic acid react in presence of sulphuric acid to give amines.145
Scholl Reaction: Coupling of aromatic molecules by treatment with Lewis acid catalysts.146
Serini Reaction: Zinc-promoted rearrangement of 17-hydroxy-20-acetoxysterol derivatives into C-20 ketones.147
Shapiro Reaction: Tosylhydrazones of aldehydes and ketones on reaction with strong bases afford alkenes organolithium compound.148
Sharpless Dihydroxylation: Osmium-catalyzed asymmetric cis-dihydroxylation of olefins.149
Sharpless Epoxidation: Titanium-catalyzed asymmetric epoxidation of allylic alcohols employing titanium alkoxide.150
Sharpless Oxyamination: Osmium-mediated cis-addition of nitrogen and oxygen moieties to mono-, di- and tri-substituted olefins to yield vicinal amino or amido alcohols.151
Simmons-Smith Reaction: This reaction affords the cyclopropanation of olefins with many organometallic compounds occurring at a surface.152
Simonini Reaction: Preparation of aliphatic esters by the reaction of the silver salt of a carboxylic acid with iodine.153
Simonis Chromone Cyclization: Formation of chromones from phenol and β-keto esters in the presence of phosphorus pentoxide.154
Sonn-Muller Method: Treatment of the anilide with phosphorus pentachloride generates the imidoyl chloride which is reduced to the imine with a mixture of stannous chloride and hydrochloric acid. Subsequent hydrolysis yields the aldehyde.155
Sonogashira Coupling: This coupling of terminal alkynes with aryl or vinyl halides is performed with a palladium catalyst, a copper (I) cocatalyst and an amine base.156
Stephen Aldehyde Synthesis: Reaction sequence employed to convert nitriles to aldehydes with a mixture of stannous chloride and hydrochloric acid yields the imine salt which is subsequently hydrolyzed to the aldehyde.157
Stevens Rearrangement: Quaternary salts containing an electron withdrawing group on the carbon attached to nitrogen atom undergo rearrangement to tertiary amines on treatment with sodamide.158
Stieglitz Rearrangement: Rearrangement of trityl hydroxylamines to Schiff bases on treatment with phosphorus pentachloride.159
Stille Coupling: The Stille Coupling is a C-C bond forming reaction between stannanes and halides.160
Stole Synthesis: Formation of indole derivatives by the reaction of arylamines with α-haloacid chlorides followed by cyclization of the resulting amides with aluminum chloride.161
Strecker Synthesis: The Strecker Synthesis is a preparation of α-aminonitriles, which are versatile intermediates for the synthesis of amino acids via hydrolysis of the nitrile.162
Strecker Sulfite Alkylation: Formation of alkyl sulfonates by reaction of alkyl halides with alkali or ammonium sulfites in aqueous solution in the presence of iodide.163
Suarez Reaction: Photoinduced conversion of hydroxyl-containing substrates with hypervalent iodine to the corresponding oxygencentered radical.164
Sugasawa Reaction: Ortho acylation of anilines by nitriles in the presence of BCl3 and an auxillary Lewis acid Mechanistic study.165
Suzuki Coupling: It is the palladium-catalysed cross coupling between organoboronic acid and halides.166
Swarts Reaction: Fluorination of organic polyhalides with antimony trifluoride in the presence of a trace of a pentavalent antimony salt.167
Swern Oxidation: This reaction allows the preparation of aldehydes and ketones from primary and secondary alcohols respectively.168
Tishchenko Reaction: The Tishchenko Reaction is a disproportionation reaction that allows the preparation of esters from two equivalents of an aldehyde.169
Traube Purine Synthesis: Preparation of 4,5-diaminopyrimidines by introduction of the amino group into the 5-position of 4-amino-6-hydroxy- or 4,6-diaminopyrimidines by nitrosation and ammonium sulfide reduction, followed by ring closure with formic acid or chlorocarbonic ester.170
Trost Allylation: Palladium-catalyzed allylation of nucleophiles.171
Trost Desymmetrization: Formation of an enantiomerically pure, azide or amine containing, five or six membered ring by a pallidium catalyzed desymmetrization using a nitrogen nucleophile.172
Ullmann Reaction: Ullmann Reaction involves the condensation of aryl halides in presence of copper at elevated temperature to give diaryls.173
Urry-Karasch rearrangement: The rearrangement is promoted by the mixture of cobaltous chloride and a Grignard reagent to give a set of rearranged product.174
Vilsmeier-Haack Reaction: It involves a convenient method for the formylation of aromatic rings with disubstituted formamides and phosphorus oxychloride.175
Voight Amination: Amination of benzoins with amines in the presence of phosphorus pentoxide.176
Volhard-Erdmann Cyclization: Synthesis of alkyl and aryl thiophenes by cyclization of disodium succinate or other 1,4-difunctional compounds with phosphorus heptasulfide.177
Von Braun Amide Degradation: This is the chemical reaction of a monosubstituted amide with phosphorus pentachloride to give a nitrile and an organohalide.178
Vorbruggen Glycosylation: The reaction of silylated heterocyclic bases with peracylated sugars in the presence of Lewis acids to yield natural β-nucleosides.179
Wacker-Tsuji Oxidation: The Wacker Oxidation allows the synthesis of ethanal from ethene by palladium-catalyzed oxidation with oxygen in presence of co-catalyst copper.180
Wagner-Jauregg Reaction: Addition of maleic anhydride to diarylethylenes with formation of bis adducts which can be converted to aromatic ring systems.181
Wagner-Meerwein rearrangement: This reaction involves the rearrangement of alkyl halides containing more than two carbon atoms in presence of AgNO3 or AlCl3.182
Walden Inversion: Inversion of configuration of a chiral center in SN2 reactions.183
Weerman Degradation: Formation of an aldose with one less carbon from an aldonic acid of the corresponding amide.184
Whiting Reaction: Alkynediols are reduced by lithium aluminum hydride in ether or tertiary amines to dienes.185
Willgerodt-Kindler Reaction: Conversion of aryl alkyl ketones to amides of the corresponding acids by aqueous ammonium polysulfide or by sulfur and a primary or secondary amine.186
Williamson Synthesis: This method is suitable for the preparation of a wide variety of unsymmetric ethers.187
Wolffenstein-Boters Reaction: Simultaneous oxidation and nitration of aromatic compounds to nitrophenols with nitric acid in the presence of a mercury salt as catalyst.188
Wolff rearrangement: α-Diazoketones on treatment with solid silver oxide split off nitrogen and rearrange to ketene.189
Woodward cis-Hydroxylation: The hydroxylation of an olefin with iodine and silver acetate in wet aceic acid to give cis-glycols.190
Wurtz Reaction: The Wurtz Coupling produces the simple dimer derived from two equivalents of alkyl halide in presence of sodium metal.191
Wurtz-Fittig Reaction: This reaction allows the alkylation of aryl halides. The more reactive alkyl halide forms an organosodium first and this reacts as a nucleophile with an aryl halide as the electrophile.192
Zincke Nitration: Replacement of ortho- or para-bromine in phenols by a nitro group on treatment with nitrous acid or a nitrite in acetic acid.193
Zincke-Suhl Reaction: Phenol-dienone rearrangement of p-cresols by addition of carbon tetrachloride in the presence of aluminum chloride with formation of 4-methyl-4-trichloromethylcyclohexa-2,5-dienone.194
CONCLUSION:
Most of the reagents discussed in this review are already known in past. Their selection for inclusion in this review was based on their versatile character which affords the preparation of a large variety of organic compounds and plays an important role in organic synthesis.
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Received on 18.04.2012 Modified on 12.05.2012
Accepted on 24.05.2012 © AJRC All right reserved
Asian J. Research Chem. 5(7): July, 2012; Page 936-960