Organic Chemistry Reaction Summary Sheet, Cheat Sheet of Organic Chemistry

Download Organic Chemistry Reaction Summary Sheet and more Cheat Sheet Organic Chemistry in PDF only on Docsity! 1 of 30| Organic Chemistry Reaction Summary Sheet Alkene Reactions Hydrohalogenation Hydrohalogenation (with Rearrangement) Halogenation Hydrobromination with Peroxide Hydration Hydration (with Rearrangement) Bromination in H2O Oxymercuration- Demurcuration Hydroboration- Oxidation Syn-Dihydroxylation Syn-Dihydroxylation Anti-Dihydroxylation Addition of an Alcohol Bromination in Alcohol Alkoxymercuration- Demurcuration Epoxidation 2 of 30| Catalytic Hydrogenation *Pt can also be used* Ozonolysis (Reducing Conditions) Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage Alkyne Reactions Catalytic Hydrogenation (Catalytic Reduction) Reduction to Cis- Alkene Reduction to Trans- Alkene Hydrohalogenation with HBr (Terminal Alkyne) Hydrohalogenation with HBr (Internal Alkyne) Halogenation with Br2 Hydration of an Internal Alkyne Hydration of a Terminal Alkyne (Markovnikov) Hydration of a Terminal Alkyne (Anti-Markovnikov) SN2 Addition of an Acetylide Ion to an Alkyl Halide SN2 Addition of an Acetylide Ion to a Ketone SN2 Addition of an Acetylide Ion to an Epoxide 1. O3 2. H2O2 or 1. KMnO4/heat 2. H3O+ O O OH H2 Lindlar’s Catalyst 5 of 30| Addition of a Grignard Reagent to an Amide Deprotonated Amide Addition of a Grignard Reagent to a Nitrile Ketone Electrophilic Aromatic Substitution (EAS) Reactions Friedel-Crafts Alkylation (Rearrangement Possible) Friedel-Crafts Acylation (No Rearrangement Possible) Bromination Chlorination Nitration Sulfonation Formylation MgX NH2 O 1. , Ether 2. H3O+ NH O MgX Cl AlCl3 Cl AlCl3 FeCl3 ClCl2 H2SO4 SO3HSO3 H2SO4/Δ MgX O1. , Ether 2. H3O+ N Cl AlCl3 OO H2SO4 NO2HNO3 AlCl3 CO, HCl O H FeBr3 BrBr2 6 of 30| EAS with an ortho/para- directing group on Benzene EAS with a meta-directing group on Benzene Friedel-Crafts Alkylation/Acylation with a meta-directing group or an amine on Benzene Benzene Side-Chain Reactions Side-Chain Oxidation of Benzene to form Benzoic Acid Wolff-Kishner Reduction Clemmensen Reduction *can also use H2/Pd, C *can also use H2/Pd, C or Sn/HCl O/P Substituent O/P O/P Substituent Substituent H2NNH2 or N2H4, -OH, Heat O Zn(Hg), HCl, Heat O Zn(Hg), HCl, Heat NH2NO2 M AlCl3 Cl R O R Cl or No Reaction NH2/NRH/NR2 AlCl3 Cl R O R Cl or No Reaction 1. KMnO4, -OH 2. H3O+, Heat O OH Na2Cr2O7 H2SO4 or R R R or or M Substituent M Substituent 1. KMnO4, -OH 2. H3O+, Heat Na2Cr2O7 H2SO4 or No Reaction (Requires free Hydrogen at Benzylic position) 7 of 30| Acetylation of Aniline using Acetic Anhydride Diazonium Salt Reactions Hydride Reduction Reactions Reduction of an Aldehyde to a 1˚Alcohol Reduction of a Ketone to a 2˚Alcohol Reduction of a Carboxylic Acid to a 1˚Alcohol Reduction of an Ester to a 1˚Alcohol NH2 H N OO O O pyridine Aniline Acetanilide NaNO2, HCl (HONO) N2+NH2 Cu Br or C uC l Br or Cl CN Cu CN I KI H 3 O + or EtO H OH F HBF 4 H3PO2 H O 1. NaBH4 2. H3O+ H OH H O 1. LiAlH4 2. H3O+ H OH O 1. NaBH4 2. H3O+ OH O 1. LiAlH4 2. H3O+ OH OH O 1. LiAlH4 2. H3O+ H OH O O 1. LiAlH4 2. H3O+ H OH OH 10 of 30| Acid-catalyzed Cleavage of Ethers when neither side is 2˚/3˚ (Nucleophile attacks less substituted side via SN2) Acid-catalyzed Ring Opening of Epoxides (Nucleophile attacks more substituted side) Base-catalyzed Ring Opening of Epoxides (Nucleophile attacks less substituted side) Aldehyde and Ketone Reactions Nucleophilic Addition to an Aldehyde or Ketone Addition of water to an Aldehyde or Ketone forming a Hydrate Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemi-acetal/Hemi-ketal Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+) Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+) Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+) O HCl OH Cl HBrO OH Br C or H O C or H HO OO HO C or H O C or H HONucleophile H3O+ Nucleophile C or H O H3O+ or -OH H2O C or H HO OH C or H O C or H O O H3O+ H3O+ HO OH C or H O C or H O O HO H3O+ H3O+ O OCH3 HOCH3 O OH C or H O C or H N H3O+ H2N H3O+ O H3O+ OH OH 11 of 30| Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H3O+) Double bond forms on more substituted end for Ketones Addition of a Wittig Reagent to an Aldehyde or Ketone Michael Addition to an α, β Unsaturated Ketone Michael Addition to an α, β Unsaturated Ketone with a Gilman Reagent (Organocuprates) Nitrile Reactions Acid-catalyzed Hydrolysis of a Nitrile SN2 formation of Nitriles using Cyanide and Alkyl Halides Cyanohydrin Formation using Aldehydes/Ketones and Cyanide OH OH3O+, HeatC N X C N C N C or H C or H C N O HO C N C or H O H3O+ N H H3O+ C or H N C or H O C or H PPh3 O O O O or -CN, HNR2, HSR etc. O O O O (CH3CH2CH2)2CuLi 12 of 30| Carboxylic Acid Derivative Reactions Alpha Addition/Substitution Reactions Self Aldol Condensation and Enone Formation Mixed Aldol Condensation and Enone Formation Self Claisen Condensation Mixed Claisen Condensation R Cl O R’OH or R’O- R‘ OH or O R‘ O O R O O Acid Anhydride O R’ R OR’ O Ester R OH O Carboxylic Acid H3O+/Heat R’OH/H+ SOCl2 H+ R2NH or R2N- R NR’2 O Amide H 3 O + /H ea t -OH R O O Carboxylate H+ H3O+ Acyl Chloride H O -OH, H2O O OH H3O+, NaOH Δ O O O O -OH, H2O O HO H3O+, NaOH Δ O O O 2 O1. 2. H3O+ O O O O O O1. 2. H3O+ O O O H O 2 -OH, H2O H O OH H3O+, NaOH Δ H O O 2 -OH, H2O O OH H3O+, NaOH Δ O 15 of 30| Halogenation What’s added: 2 Br atoms Regioselectivity: N/A Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism: Hydrobromination with Peroxide What’s added: H× and Br× Regioselectivity: Anti-Markovnikov Stereoselectivity: N/A Intermediate: Radical Rearrangement: Not possible Mechanism: 16 of 30| Hydration What’s added: H+ and OH- Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism: Bromination in H2O What’s added: Br+ and OH- Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism: Oxymercuration-Demercuration What’s added: H+ and OH- Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion bridge Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction 17 of 30| Hydroboration-Oxidation What’s added: H+ and OH- Regioselectivity: Anti-Markovnikov Stereoselectivity: Syn Intermediate: Hydroxy-boranes Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Syn-Dihydroxylation or What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism: Anti-Dihydroxylation What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Anti Intermediate: N/A Rearrangement: Not possible Mechanism: Epoxidation then reaction with aqueous acid or base. In acidic conditions, the H2O attacks the more highly-substituted C: In basic conditions, H2O attacks the less highly-substituted C: 20 of 30| Ozonolysis in Oxidizing Conditions/Oxidative Cleavage What’s added: Multiple O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction Know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Any H’s attached to the alkene C’s get replaced by an –OH group since we are under oxidizing conditions/hot KMnO4. Unlike reducing conditions which would have formed aldehydes, oxidizing conditions produces carboxylic acids instead. Alkyne Reaction Details Catalytic Hydrogenation What’s added: 4 H atoms Regioselectivity: N/A Stereoselectivity: Anti Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction. Note: You may see Pt used as well. This is just the catalyst and does not change the outcome of the products. Reduction to Cis-Alkene 1. O3 2. H2O2 or 1. KMnO4/heat 2. H3O+ O O OH 1. O3 2. H2O2 or 1. KMnO4/heat 2. H3O+ O O OH H2 Lindlar’s Catalyst What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction 21 of 30| Reduction to Trans-Alkene What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity: Anti Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Hydrohalogenation with HBr (Terminal Alkyne) What’s added: 1 H atom and 1 halogen atom (can be F, Br, I, or Cl) per equivalent of HX Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Not possible Mechanism: The halogen goes to the C with fewer H’s Hydrohalogenation with HBr (Internal Alkyne) What’s added: 1 H atom and 1 halogen atom (can be Cl or Br) per equivalent of HX Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Not possible Mechanism: Same as for terminal alkynes, but yields a mixture of two products because both intermediates are equally stable 22 of 30| Halogenation with Br2 What’s added: 2 halogen atoms (can be F, Br, I, or Cl) Regioselectivity: N/A Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism: Hydration of an Internal Alkyne What’s added: 1 O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that this reaction produces enols, which then tautomerize to form ketones. Hydration of a Terminal Alkyne (Markovnikov) What’s added: 1 O atom Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that this reaction produces Markovnikov enols, which then tautomerize to form ketones. OH O enol (Markovnikov) ketone tautomerism 25 of 30| Ozonolysis/Oxidative Cleavage on a Terminal Alkyne What’s added: 4 O atoms and 1 H atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Don’t worry about it! J Rearrangement: Not possible Mechanism: Don’t worry about it! J Know that the reaction cuts the triple bond in half. On the internal side, an O replaces two of the bonds as C=O and the third lone bond becomes a bond to -OH. On the terminal side, two oxygens O replaces all the bonds on carbon, forming the most oxidized form of carbon: CO2. 1. O3 2. H2O2 or 1. KMnO4/heat 2. H3O+ O OH CO2 Terminal carbon becomes CO2 1. O3 2. H2O2 or 1. KMnO4/heat 2. H3O+ O OH CO2 Terminal carbon becomes CO2 26 of 30| Free Radical Halogenation Reaction Details Free Radical Halogenation using Bromine (more selective) What’s added: 1 Br atom Regioselectivity: Most Substituted Product Stereoselectivity: N/A Intermediate: Radical Intermediate Rearrangement: Not possible Mechanism: Formation of bromine and carbon radicals and them joining to create an alkyl halide 1. Initiation 2. Propagation 3. Termination Free Radical Halogenation using Chlorine (less selective) What’s added: 1 Cl atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Radical Intermediate Br Br hv or Δ Br Br Br Br Br Br Cl2 hv or Δ Cl Cl Cl Cl Br2 hv or Δ Br H Br HBr Br Br Br Br alkyl halide 27 of 30| Rearrangement: Not possible Mechanism: Formation of chlorine and carbon radicals and them joining to create alkyl halides 1. Initiation 2. Propagation 3. Termination Allylic/Benzylic Bromination Cl Cl hv or Δ Cl Cl Cl HCl Cl Cl Cl alkyl halide H Cl Cl HCl Cl Cl Cl alkyl halide Cl H Cl Cl Cl Cl NBS hv or Δ or ROOR Br NBS hv or Δ or ROOR Br Br H Cl HCl Cl Cl Cl Cl alkyl halide Cl HCl Cl Cl Cl alkyl halide Cl H