重要经典化学反应及其机理.doc

- Aromatic Reactions - Condensation - Cyclization -Epoxide Transformation - Olefination - Oxidation - Reduction - Rearrangement Condensation OlefinationOxidationRearrangementReductionCyclizationAromatic Reactions topCommon Transformation of Epoxide top.a recent memoir by a Herr vant Hoff on the Arrangements of Atoms in Space, a document crammed to the hilt with the outpourings of a childish fantasy.This Dr. J.H. vant Hoff.no taste for accurate chemical research. By H. Kolbe (one of the most eminent organic chemist of the time). 10 years later vant Hoff was named the first recipient of the Nobel Prize in Chemistry.AAcetoacetic Ester Synthesis is a very useful basic reaction in ether industry or academia. The methylene group in acetoactic ester could be easily alkylated, and double alkylated under basic condition. One condition I used frequently is acetone as solvent, K2CO3 as base, and alkyl bromide as alkylation reagent. The reaction rarely lets me down. Simonsen, J.L.; Storey, R. J. Chem. Soc. 1910, 95, 2106Simonsen, J.L.; Storey, R. Proc. Chem. Soc. 1910, 25, 290 Click here to learn more. Alder (Ene) Reaction is thermal or catalytic sigmatropic rearrangement with H-trasfer and carbon bond formation. Click here to learn more.Aldol condensation is a reaction that generated lots of Ph.D. in organic synthesis. No need to talk about it. The aldol condensation using aldehyde and silyl enol ether as starting materials, and lewis acid, like TiCl4, as catalyst is called Mukaiyama aldol condensation. Kane, R. Ann. Phys. Chem. Ser. 2 1838, 44, 475Kane, R. J. Prakt. Chem. 1838, 15, 129 Click here to learn more.Algar-Flynn-Oyamada Reaction is the synthesis of flavonols via the intermediate dihydroflavonols made by oxidation of o-hydroxyphenyl styryl ketone using hydrogen peroxide. Click here to learn more.Allen-Millar-Trippet rearrangement. Click here to learn more.Amadori Rearrangement is the conversion of N-glycosides of aldoses to N- glycosides of the corresponding ketones. Click here to learn more.Angeli-Rimini hydroxamic acid synthesis Click here to learn more.Appel Halogenation Click here to learn more.Arndt (Fritz Arndt 1885-1969) -Eistert (Bernd Eistert 1902-1978) rearrangement is used in the conversion of a carboxylic acid into its homolog or derivatives of the homologous acid. If the reaction intermediate could be quenched to give alpha-halo ketone. Click here to learn more.Asinger Thiazoline Synthesis Click here to learn more.Auwers reaction is the expansion of coumarones to flavonols. K. v. Auwers et al., Ber. 41, 4233 (1908); 48, 85 (1915); 49, 809 (1916)K. v. Auwers and P. Pohl, Ann 405, 243 (1914)Click here to learn more.Azo coupling Click here to learn more.B C topBaeyer Pyridine Synthesis Click here to learn more.Baeyer (Johann Friedrich Wilhelm Adolf von Baeyer 1835 - 1917) -Villiger (Victor Villiger 1868 - 1934) Oxidation is an oxidative rearrangement reaction initiated by nucleophilic attack. The order of migratory aptitude is 3o-alkyl 2o-alkyl benzyl phenyl 1o-alkyl cyclopropyl MeH. If it is used in phenyl aldehyde to make phenol, the reaction is called Dakin oxidation. Click here to learn more. Johann Friedrich Wilhelm Adolf von Baeyer, Nobel Prize Chemistry 1905.Baker (Wilson Baker b.1900) -Venkataraman rearrangement is the rearrangement of o-keto ester of phenol to o-hydroxy-1,3-diketone. The 1,3-diketone could cyclize to form flavone. Click here to learn more.Bamberger (Eugen Bamberger 1857-1932) rearrangement is the intermolecular rearrangement of N-phenylhydroxlamines to the corresponding 4-aminophenol under acidic condition. Click here to learn more.Bamberger imidazole cleavage Click here to learn more.Bamford (W. R. Bamford) -Stevens-Shapiro Olefination is a base-catalyzed decomposition of arenesulfonylhydrazones of aldehydes and ketones, leading to the formation of alkenes. Click here to learn more.Barbier (Francois Antoine Phillipe Barbier 1848-1922) Reaction is the one-pot procedure for the preparation of alcohols from organic halides and aldehydes or ketones. Click here to learn more.Bargellini reaction is using a ketone and CHCl3 generate a dichloro epoxide, which react with a hydroxyl amine or diamnio ethane derivative to form highly hindered morpholinone or piperazinone. Click here to learn more.Bartoli (Giuseppe Bartoli) indole synthesis is the synthesis of indoles reductively by o-substituted nitrobenzene and allyl grignard. Click here to learn more.Barton (Derek H. R. Barton1928 -1998) deamination Click here to learn more.Barton decarboxylation Click here to learn more.Barton deoxygenation is the deoxygenation of alcohols via their thiocarbonyl derivatives. Click here to learn more.Baylis (A.B. Baylis) - Hillman (M.E.D. Hillman) Reaction is the activated vinyl system to react with ketone or aldehyde to yield alpha-hydroxyl products. Click here to learn more.Beckmann (Ernst Otto Beckmann 1853 -1923) Rearrangement is acid (P2O5, PCl5, H2SO4 etc) catalyzed rearrangement of oxime to amide or nitrile. Click here to learn more.Benzilic acid rearrangement is base-induced rearrangement of benzil to benzylic acid via phenyl group migration. Liebig, J. Ann. Chem. 1838, 25, 27Zinin, N. Ann. Chem. 1839, 31, 329 Click here to learn more.Benzoin Condensation is cyanide-catalyzed condensation of aromatic aldehydes to give benzoins. Lapworth, A.J. J. Chem. Soc. 1903, 83, 995Lapworth, A.J. J. Chem. Soc. 1904, 85, 1206 Click here to learn more.Bergman (Robert George Bergman) Cyclization is the cyclization of enediynes to generate 1,4-benzenoid diradicals. Click here to learn more.Bernthsen Acridine Synthesis is the synthesis of 5-substituted acridines by diarylamines in organic acids or anhydrides. Click here to learn more.Biginelli pyrimidone synthesis is the 3 components formation of tetrahydropyrimidinones. Click here to learn more.Bischler - Mohlau indole synthesis is the formation of 2-substituted indoles by heating alpah-halo or hydroxy-ketone with excess amount of aniline. The excess amount aniline is highly important for the success of reaction and mechanism. This is a proposed mechanism from a experienced colleague. Click here to learn more.Bischler (August Bischler 1865 - ?) - Napieralski (Bernard Napieralski ) Isoquinoline synthesis. Bischler - Napieralski reaction is similar to Morgan -Walls reaction (Pictet - Hubert reaction). Click here to learn more.Blanc-Quellet chloroalkylation Click here to learn more.Blicke-Pachter Pteridines synthesis Click here to learn more.Blum Aziridine synthesis Click here to learn more.Boekelheide reaction Click here to learn more.Boger pyridine synthesis is a hetero Diels-Alder reaction. Click here to learn more.Bouveault aldehyde synthesis Click here to learn more.Brandi-Guarna rearrangement Click here to learn more.von Braun reaction is the degradation of a tertiary amine with cyanogen bromide or chloroformate. Click here to learn more.Brook (Adrian Gibbs Brook 1924 - ) Rearrangement Click here to learn more.Brown hydroboration not only could make hydroxyl group but also could make amino group. Brown, H.C.; Subba Rao, B.C. J. Am. Chem. Soc. 1956, 78, 5694Brown, H.C.; Subba Rao, B.C. J. Org. Chem. 1957, 22, 1135; 1136 J. Org. Chem. 1981, 46, 4296; J. Am. Chem. Soc. 1964, 86, 3565. Click here to learn more.Bruylants amination Click here to learn more.Bucherer (Hans Theodor Bucherer 1869-1949) - Bergs Hydantoin synthesis Click here to learn more.Buchner-Curtius homologation Click here to learn more.Burgess dehydrating reagent Click here to learn more.C B topCannizzaro (Stanislao Cannizzaro 1826 - 1910) disproportination reaction tells that aldehyde is not very stable under basic condition. Click here to learn more.Carroll rearrangement Click here to learn more.Chapman (Arthur William Chapman 1898 - ?) rearrangement Click here to learn more.Chichibabin (Alexei Yevgenievich Chichibabin 1871 -1945) pyridine synthesis Click here to learn more.Chugaev (Lev Aleksandrovich Chugaev 1873 - 1922) elimination is the hydroxyl group reacts with CS2, followed by methylation to form xanthate. The smell of this reaction is not very good, because it will release methyl thiol. Click here to learn more.Ciamician-Dennstedt cyclopropanation. Ciamician-Dennstedt rearrangement is the rearrangement of cyclopropane formed from dichlorocarbene. Click here to learn more.Claisen-Geuter-Dieckmann ester condensation Click here to learn more.Claisen (Rainer Ludwig Claisen 1851-1930) - Ireland Rearrangement is a 3,3 sigmatropic shift. Click here to learn more.Clarke (Hans Thacher Clarke 1887 - 1927) - Eschweiler reductive amination is especially for the methylation of amino group, another reductive amination reaction with similar mechanism iscalled Leuckart-Wallach reaction that ketone or high level aldehyde is used instead of fomaldehyde. NaBH3CN is also used in reductive amination under mild acidic condition. Click here to learn more.Clauson-Kaas Pyrrole synthesis Click here to learn more.Combes quinoline synthesis Click here to learn more.Comins reaction Click here to learn more.Conrad-Limpach reaction Click here to learn more.Cook-Heilbron thiazole synthesis Click here to learn more.Cope elimination reaction is the syn-elimination of N-oxides of tertiary amines. You can compare this reaction with another elimination, Hofmann elimination, in which a quaternary ammonium slat undergoes elimination to form less substituted olefin. The leaving hydrogen is more acidic or less hindered. Hofmann elimination was used a lot in early stage alkaloid structure identification. Click here to learn more.Cope (Arthur Clay Cope 1909 - 1966) Rearrangement is the conversion of a 1,5-hexadiene derivative by the 3,3-sigmatropic mechanism. The reaction is both stereospecific and stereoselective. Click here to learn more.Corey (Elias James Corey 1928 - ) - Bakshi - Shibata Reduction, oxazaborolidine (CBS reagent), is used to reduce a ketone enantioselectively by borane. The catalyst can be made from L-proline or D-proline. You can buy commercially available catalysts from Aldrich. The enantioselectivity is obtained by the different steric hinderance between large and small groups in ketone. Corey, Nobel Prize Chemistry 1990. Click here to learn more.Corey-Chaykovsky sulfur ylide reaction Click here to learn more.Corey - Kim (A.U. Kim) Oxidation Click here to learn more.Corey-Link reaction Click here to learn more.Corey-Seebach reaction Click here to learn more.Corey - Winter (Roland Arthur Edwin Winter 1935 - ) olefination is the synthesis of alkenes from vicinal diols. This method has been particularly useful in synthesizing substrates with delicate structure features such as strained and twisted olefins, unsaturated carbohydrates, macrocyclic lactones, as well as in establishing the stero-chemistry of diol functions in natural products. Click here to learn more.Cornforth (John Warcup Cornforth 1917 - ) oxazole rearrangement Click here to learn more. Cornforth, Nobel Prize Chemistry 1975Criegee (Rudolf Criegee 1902 - 1975) ozonolysis is a very clean reaction. Criegee glycol oxidation is the oxidation of 1,2-glycol to two carbonyl by lead tetraacetate (LTA). Click here to learn more.Curtius (Theodor Curtius 1857-1928) rearrangement Click here to learn more.B CDDakin (Henry Drysdale Dakin 1880 - 1952) reaction Dakin-West reaction Danshiefsky (Samuel J. Danishefsky 1936 - ) diene Darzens (George Darzens 1867 - 1954) reaction is a alpha halo ester to react with a ketone or aldyhyde give a glycidic ester with an epoxide ring. Davis Oxidizing reagent is the camphorylsulfonyl oxaziridine derivative used to do enatio-selectively alpha-hydroxylation of carbonyl compounds. Compare with Oppolzer chiral auxiliary. Davidson oxazole synthesis de Kimpe amidine synthesis De Mayo cycloaddition is the synthesis of 1,5-diketones. Delepine (Stephane Marcel Delepine1871 - 1965) Amine syntheisis Demjanov (Nikolai Jakovlevich Demjanov 1861 - 1938) rearrangement is a carbon cation rearrangement generated by an amine and nitrous acid. This reaction appears to be useful to preparation of five, six, and seven membered rings, and to be less valuable for the preparation of smaller or larger rings. Dess (D.B. Dess) - Martin (James Cullen Martin 1928 - ) Oxidation reagent is a periodinane reagent to oxidize the alcohol to aldehyde or ketone. The red intermediate is very easy to decompose, explosion is a potential hazard. The same type of oxidation reagent is IBX. Dieckmann (Walter Dieckmann 1869 - 1925) (Claisen) ester condensation is the sythesis of open or cyclic beta-keto esters. This reaction is similar to base-catalyzed Aldol condensation. Diels (Otto Paul Hermann Diels 1876 - 1954) - Alder (Kurt Alder, July 10, 1902- June 20, 1958) cycloaddition is one of most studied reactions, and huge number of organic chemistry Ph.D.s are generated from this reaction. No need to talk any more. Diels and Kurt Alder, Nobel Prize Chemistry 1950.Dimroth triazole synthesis Dimroth rearrangement Molecules 2001, 6, 574-587Doebner (Oscar Doebner 1850 - 1907) quinoline synthesis Dondoni homologation Dornow-Wiehler isoxazole synthesis Down ring expansion E F G H I J K topEhrlich-Sachs Aldehyde synthesis Eschenmoser coupling reaction the synthesis of enamino ketones from thioamides or beta-dicarbonyl derivatives from thioesters. Eschenmoser-Tanabe fragmentation Eschweiler (Wilhelm Eschweiler 1860 - 1936) - Clarke (Hans Thacher Clsrke) amine methylation F E G H I J K topFavoskii (Alexei Yevgrafovich Favorskii 1860 - 1945) Rearrangement is alpha-haloketone undergoes a skeleton change under basic conditions. The common product of this reaction is acid or ester. Feist-Benary furan synthesis Ferrario-Akermann thiocyclization Finegan tetrazole synthesis Finkelstein (Hans Finkelstein 1885 - 1938) reaction Fisher-Hepp rearrangement Fisher (Emil Hermann Fischer 1852-1919) indole synthesis Forster diazo synthesis Forster - Decker amine synthesis Freidel (Charle Friedel 1832 - 1899) -Crafts (James Mason Crafts 1839 - 1917) reaction Friedlander (Paul Friedlander 1857 - 1923) quinoline synthesis Fujimoto-Belleau cyclohexenone G E F H I J K topGabriel (Siegmund Gabriel 1851 - 1924) amine synthesis Garigipati amidine synthesis Gassman indole synthesis Gewald aminothiophene synthesis. This proposed mechanism is from Lab Rat experience. Gilman-van Ess ketone synthesis Gomberg (Moses Gomberg 1866 - 1947) - Bachmann (Werner Emmanuel Bachmann 1901-1951) reaction Graham (William Hardin Graham 1932 - ) diazirine synthesis Granacher Homologation Grob (Cyril A. Grob 1917 - ) fragmentation Guaresky-Thorpe 2-pyridone synthesis is the formation of pyridone from beta-diketone and activated amide. H E F G I J K topHajos-Parrish alodol cyclization Haller-Bauer ketone cleavage Hantzsch thioazole synthesis Hantzsch (Arthur Rudolf Hantzsch 1857 - 1935) pyridine synthesis is an one pot reaction to make pyridine from a beta-keto ester, a aldehyde, and ammonia. Hantzsch Pyrrole synthesis Hassner aziridine - azirine synthesis Hassner-Rubottom alpha-hydroxylation Hauser-Beak directed ortho lithiation Hell (Carl Magnus von Hell 1849 - 1926) - Volhardt (Jacob Volhard 1834 - 1910) - Zelinski bromination Henry (Louis Henry 1834 - 1913) reaction is the condensation between nitro alkanes and ketones or aldehydes. Herz benzothiazole synthesis Hinsberg thiophene synthesis Hiyama aminoacrylate Hoch-Campbell aziridine synthesis Hofmann (August Wilhem von Hofmann 1818 - 1892) rearrangement Click here to learn more ( Hofmann tree)Hofmann (August Wilhem von Hofmann 1818 - 1892) elimination Hofmann (August Wilhem von Hofmann 1818 - 1892) - Loffler (Karl Loffler 1878 - 1910) - Freytag (Curt Freytag) reaction Horner-Wadsworth-Emmons Olefination is a Wittig type