Key named reactions in organic chemistry · 2020. 10. 4. · Electrophilic addition reactions...
Transcript of Key named reactions in organic chemistry · 2020. 10. 4. · Electrophilic addition reactions...
Knorr pyrrole synthesisL. Knorr Heterocycle formation Used to create substituted pyrroles through reacting an α-amino-ketoneand a compound containing an electron-withdrawing groupe.g. an ester to a carbonyl group.
1887Gabriel synthesisS. Gabriel Nucleophilic substitutionreactions Traditionally usingpotassium phthalimide transforms primary alkyl halides into primary amines.
1887Reformatsky reactionS. Reformatsky Reactions involving carbonylcompounds Condenses aldehydes or ketones with α-halo esters using metallic zinc to form β-hydroxy-esters.
1893Pomeranz-Fritsch reactionC. Pomeranz andP. Fritsch Heterocycle formationCondensation of benzaldehydes or arylketones with aminoacetalde-hyde acetals, it is used tosynthesize isoquinolines.
1894KnoevenagelcondensationE. Knoevenagel Reactions involvingcarbonyl compounds Often used to generateα,β-unsaturated ketones through nucleophilic addition of an active hydrogencompound to a carbonyl group followed by adehydration reaction in which a molecule of water iseliminated.
1897Gattermann andGattermann-Koch formylation L. Gattermannand J.A. Koch Electrophilic aromatic substitution reactions Creation of a formyl(aldehyde) functionality by treating with a mixture of hydrogen cyanide (HCN) and hydrogen chloride (HCl)in the presence of a Lewis acid catalyst such as AlCl3.
1899Baeyer-Villiger
oxidation A. Baeyer
and V. VilligerNucleophilic substitution
reactions Generation of an ester from
a ketone or a lactone from a cyclic ketone using
peroxyacids or peroxides.
1886
1900Fries rearrangementK. Fries and colleagues Electrophilic aromaticsubstitution reactionsPreperation of hydroxy aryl ketones through transformation of phenolic esters via Lewis acid catalysis.
1900Grignard reactionV. Grignard Reactions involving carbonyl compounds Some important applicationsare the synthesis of alcohols,aldehydes or ketones,monocarboxylic acids, andother organometallic ororganometalloid compoundsvia organo magnesiumintermediates.
1901Ullmann reactionF. Ullmann Transition metal-catalyzed couplings Traditionally the Ullmann reaction refers to the synthesis of symmetric biaryls viacopper-catalyzed coupling at high temperatures(200 °C).
1906TishchenkoreactionV. E. Tishchenko Nucleophilic substitution reactions Catalysed by aluminium alkoxides or sodiumalkoxides generatesthe ester from thecorresponding aldehyde.
1909Prilezhaev reactionN.A. Prilezhaev Electrophilic addition reactions Reaction of an alkene with a peroxy acid (often meta-chloroperoxyben-zoic acid (m-CPBA), due to its stability and good solubility in most organic solvents) to form epoxides.
1911Pictet-SpenglertetrahydroisoquinolinesynthesisA. Pictet and T. Spengler Heterocycle formation An important acid-catalyzed transformation for the synthesis of tetrahydroisoquinolines from carbonyl compounds andβ-arylethylamines.
1911Wolff–KishnerreductionN. Kishnerand L. Wolff Reduction reactions Converts carbonyl functionalities into alkanes. It is often used to remove a carbonyl group after it has served its synthetic purpose of activating anintermediate in a preceding step.
1913Clemmensen reductionE.C. Clemmensen Reduction reactions Reduces aldehydes or ketones to alkanes in the presence of zinc amalgam and concentratedhydrochloric acid.
1915Houben-HoeschsynthesisK.Hoesch and J. Houben Electrophilic aromatic substitution reactions This reaction is a type of Friedel-Crafts acylation withhydrogen chloride and a Lewis acid catalyst to prepare an aryl ketone from reaction of a nitrile with an arene compound.
1917Mannich reactionC. Mannich Reactions involving carbonyl compounds Formation of a β-amino-carbonyl compound, also known as aMannich base, through amino alkylation of an acidic proton nextto a carbonyl containing functional group by formaldehyde and a primary or secondary amine or ammonia.
1919Wohl-Ziegler brominationA. Wohl andK. Ziegler Free radical reactionsGenerates allylic and benzylic bromides through allylic or benzylic bromination of hydrocarbons using the reagentN-bromosuccinimide combined witha radical initiator.
1919Staudinger reactionH. Staudinger and J. Meyer Reduction reactions Creates primary amines via the reaction between an azide and phosphine, which form a reactive aza-ylide as an intermediate that is hydrolyzed spontaneously.
1926Meerwein–Ponndorf–Verley reductionH. Meerwein,W. Ponndorf andA. Verley Reduction reactions Hydrogenation which does not require the use of hazardouspressurized H2 but utilizesavailable, inexpensive, and easy-to-handle hydrogen donor molecules to carry out thesubstrate hydrogenation.
1937Oppenauer
oxidationR.V. Oppenauer
OxidationSelective oxidation of
secondary alcohols to ketones reaction takes place
in the presence of [Al(i-PrO)3] in an excess of
acetone.
1937Overman rearrangementL. Overman Pericyclic and photochemical reactions Generating allylic trichloroacetamides through an imidate intermediate from allylic alcohols it has found application inasymmetric synthesis.
1939Hunsdiecker reactionC. and H. Hunsdiecker Free radical reactionsForms alkyl bromides via the decarboxylation of mercury or silver salts of carboxylic acids by treating with bromine. The alkyl bromide contains one fewer carbons than the carboxylic acid.
1939MeerweinarylationH. Meerwein Free radical reactionsA powerful tool for the diverse functionalization of alkenes through addition of an aryl diazonium salt (ArN2X) to an electron-poor alkene usually supported by a metal salt.
1941Nazarov cyclizationN. Nazarov Pericyclic andphotochemical reactions Used in the synthesis ofcyclopentenones from divinyl ketones, it is a powerful tool to create 5-membered rings.
1946Jones oxidationE.R.H. Jones and colleagues OxidationUsed to convert primary alcohols into carboxylic acids or secondary alcohols into ketones using chromic acid (Jones Reagent).
1950Wittig reactionG. Wittigand G. Geissler Reactions involving carbonyl compounds Preparation of alkenes through reaction of an aldehyde or ketone with a triphenyl phosphoniumylide (often called a Wittig reagent).
1954Paterno-Büchi reaction
E.P. di Sessa and G.H. Büchi Pericyclic and photochemical reactions
Formation of oxetanes through thephotochemical [2+2] cycloaddition of a
carbonyl with an alkene.
1958Simmons–Smith
cyclopropanationH.E. Simmons Jr.
and R.D. SmithElectrophilic addition
reactions Creation of a cyclopropane
ring via an organozinc carbenoid that reacts with
an alkene (or alkyne).
1964Eschenmoser - ClaisenrearrangementA. Eschenmoser Pericyclic and photochemical reactionsProduces a γ,δ-unsaturated amide when an allylic alcohol is heated with N,N-dimethylacetamide dimethyl acetal.
1967Mitsunobu reaction
O. MitsunobuNucleophilic substitution
reactions Converts an alcohol into a
variety of functional groups, such as an ester, using
triphenylphosphine and an azodicarboxylate such as
diethyl azodicarboxylate (DEAD) or diisopropyl
azodicarboxylate (DIAD).
1968Mislow-Evans rearrangementK. Mislow and D. Evans Pericyclic and photochemical reactionsA general application for the preparation of trans-allylic alcohols from allylic sulfoxides in a 2,3-sigmatropic rearrangement.
1970Heck reactionT. Mizoroki and
R.F. Heck Transition metal-catalyzed
couplings Used frequently in the synthesis of
heterocyclic compounds the reaction of aryl halides or vinyl halides with
activated alkenes in the presence of a Palladium-catalyst along with a
base for C-C bond formation.
1974Rubottom oxidationG.M. Rubottom, A.G. Brookand A. Hassner OxidationUsed for the synthesis of α-hydroxy ketones through reaction of silyl enol ethers with mCPBA, and subsequent rearrangement.
1974SchwartzhydrozirconationD.W. Hart andJ. Schwartz Electrophilic addition reactions Describes the use of the reagent Zirconocene hydrochlorideotherwise known as zirconocene chloride hydride, a metallocene used for various transformations of alkenes and alkynes.
1976Negishi cross-couplingreactionE. NegishiTransition metal-catalyzed couplings The Negishi reaction is the coupling of organozinc compounds catalysed by Pd or Ni catalyst.Typically ArZnX + RX ---> Ar-R + ZnX2
1978Swern oxidationD.Swern and co-workers Nucleophilic substitution reactions A mild oxidation that converts a primary or secondary alcohol to the corresponding aldehyde or ketone using oxalyl chloride, dimethyl sulfoxide (DMSO) and an organic base, such as triethylamine.
1978Stille cross-coupling reactionJ.K. Stille Transition metal-catalyzed couplings Palladium catalyzed carbon-carbon bond formation via the coupling of an organotin compound with a variety of organicelectrophiles.
1979Suzuki cross-coupling reactionA. Suzuki Transition metal-catalyzedcouplings Palladium catalyzed carbon-carbon bond formation where the coupling partners are a boronic acid/ester or equivalent and an organohalide.
1978Luche reductionJ.L. Luche Reduction reactions The selective organic reduction of α, β-unsaturated ketones to allylic alcohols with sodium borohydride (NaBH4) and lanthanide chlorides, such as cerium(III) chloride (CeCl3), in methanol or ethanol.
1980SharplessasymmetricepoxidationK.B. Sharplessand T. Katsuki OxidationUsed to prepare2,3-epoxyalcohols from primary and secondaryallylic alcohols. The reaction is catalyzed via a mixture of titanium tetra(isopropoxide) and diethyl tartrate.
Dess–MartinoxidationD.B. Dess andA. Martin OxidationOxidation of primary alcohols to aldehydes and secondary alcohols to ketones via use of the Dess–Martin periodinane (DMP) reagent.
1983
1980Noyori asymmetrichydrogenationR. Noyori Electrophilic addition reactions The asymmetric hydrogenation of aldehydes, ketones and imines catalyzed by Ru(II)-BINAP and related ruthenium complexes.
1996Shi asymmetricepoxidationY. Shi Electrophilic additionreactions Synthesis of epoxides from various alkenes using afructose-derived organocatalyst with Oxone as the primary oxidant.
1884Sandmeyer reaction
T. SandmeyerFree radical reactions Generates an
aryl halide from the corresponding aryl diazonium salt using copper salts as
catalysts or reagents.
1882Hantzsch
dihydropyridine synthesis
A. HantzschHeterocycle formation
Produces1,4-dihydropyridines
(DHPs), or “Hantzsch esters”, as isolable
intermediates that can then be oxidized to pyridines.
1883
1877Friedel-Crafts acylation and alkylation reactionC. Friedel and J.M. CraftsElectrophilic aromatic substitution reactions Acylation or alkylation of an aromatic ring via reaction with an acyl or alkyl halide in the presence of a strong Lewis acid typically aluminium chloride.
Fischer indole synthesisE. Fischerand F. JourdanHeterocycle formation Generates aromatic heterocycle indole from a (substituted) phenylhydrazine and an aldehyde or ketone under acidicconditions.
1973Keck radical allylationM. Kosugi and J. Grignon Free radical reactionsUsed for the conversion ofaldehydes into homoallylic alcohols.
1953NobelPrize Winner
2010NobelPrize Winner
2001NobelPrize Winner
1902NobelPrize Winner
1905NobelPrize Winner
1912NobelPrize Winner
1963NobelPrize Winner
1979NobelPrize Winner
2010NobelPrize Winner
2010NobelPrize Winner
2001NobelPrize Winner
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Key named reactions in organic chemistry1870 2000
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2020
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