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Alkene, Alkyne, Diels Alder, Grignard, EAS, Diazonium Salt, Hydride Reduction and many more reactions are here
Typology: Cheat Sheet
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Hydrohalogenation
Hydrohalogenation (with Rearrangement)
Halogenation
Hydrobromination with Peroxide
Hydration
Hydration (with Rearrangement) Bromination in H 2 O
Oxymercuration- Demurcuration
Hydroboration- Oxidation
Syn-Dihydroxylation
Syn-Dihydroxylation
Anti-Dihydroxylation
Addition of an Alcohol
Bromination in Alcohol
Alkoxymercuration- Demurcuration
Epoxidation
Catalytic Hydrogenation Pt can also be used Ozonolysis (Reducing Conditions)
Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage
Catalytic Hydrogenation (Catalytic Reduction) Reduction to Cis- Alkene Reduction to Trans- Alkene Hydrohalogenation with HBr (Terminal Alkyne) Hydrohalogenation with HBr (Internal Alkyne) Halogenation with Br 2
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 SN 2 Addition of an Acetylide Ion to an Epoxide
Lindlar’s Catalyst
Diene Addition to a trans Dienophile
Diene Addition to a substituted Dienophile
Addition of a Grignard Reagent to an Aldehyde 2˚Alcohol
Addition of a Grignard Reagent to a Ketone 3˚Alcohol
Addition of a Grignard Reagent to an Ester 3˚Alcohol
Addition of a Grignard Reagent to an Acyl Chloride
3˚Alcohol Addition of a Grignard Reagent to CO 2
Carboxylic Acid
Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side)
Addition of a Grignard Reagent to a Carboxylic Acid
Carboxylate
hv or
enantiomers
hv or
endo (Major)
exo (Minor)
MgX OH
MgX
MgX
MgX O
O (^) 1. 2 eq. , Ether
MgX Cl
O (^) 1. 2 eq. , Ether
Addition of a Grignard Reagent to an Amide
Deprotonated Amide
Addition of a Grignard Reagent to a Nitrile Ketone
Friedel-Crafts Alkylation (Rearrangement Possible)
Friedel-Crafts Acylation (No Rearrangement Possible)
Bromination
Chlorination
Nitration
Sulfonation
Formylation
MgX NH (^2)
MgX
Cl AlCl (^3)
Cl AlCl (^3)
FeCl (^3)
Cl Cl 2
MgX
Cl AlCl (^3)
3
AlCl (^3)
CO, HCl
FeBr 3
Br2 Br
Acetylation of Aniline using Acetic Anhydride
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
pyridine Aniline Acetanilide
NaNO 2 , HCl (HONO)
CuBr or CuCl Br or Cl
CuCN
or EtOH
4
O (^) 1. NaBH (^4)
O (^) 1. LiAlH (^4)
O (^) 1. NaBH (^4)
O (^) 1. LiAlH (^4)
O (^) 1. LiAlH (^4)
O (^) 1. LiAlH (^4)
Reduction of an Ester to an Aldehyde
Reduction of an Acyl Chloride to a 1˚Alcohol
Reduction of an Acyl Chloride to an Aldehyde
Reduction of an Amide to an Amine
Hoffmann Rearrangement
Reduction of a Nitrile to an Amine
Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN 1
Conversion of a 1˚/2˚Alcohol to an alkyl bromide via SN 2
Conversion of a 1˚/2˚Alcohol to an alkyl chloride via SN 2
Conversion of an Alcohol to a Tosylate Ester (OTs) Retention of Stereochemistry
Acid-catalyzed Dehydration of an Alcohol Zaitsev’s Rule
Cl
O (^) 1. LiAlH (^4)
O (^) 1. LiAlH (^4)
OH (^) PBr 3 Br
O LiAlH[OC(CH 3 ) 3 ] 3 Cl
OH (^) SOCl 2 Cl Pyridine
OH (^) PBr 3 H
Br
OH (^) SOCl 2 H
Cl Pyridine
OH (^) TsCl OTs
O (^) 1. Br 2
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)
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 H 3 O+)
Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H 3 O+)
Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H 3 O+)
O HCl OH
Cl
O (^) HBr OH Br
C or H
C or H
C or H
C or H
Nucleophile HO H 3 O+
Nucleophile
C or H
H 3 O+^ or - OH
C or H
C or H
C or H
C or H
C or H
C or H
C or H
Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H 3 O+)
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)
Acid-catalyzed Hydrolysis of a Nitrile
SN2 formation of Nitriles using Cyanide and Alkyl Halides
Cyanohydrin Formation using Aldehydes/Ketones and Cyanide
C N^3 O+, Heat
C or H C or H
C or H
C or H
C or H
C or H
PPh (^3)
or -^ CN, HNR 2 , HSR etc.
O
(CH 3 CH 2 CH 2 ) 2 CuLi
Dieckmann Cyclization (Intramolecular Claisen Condensation) Acetoacetic Ester Synthesis
Malonic Ester Synthesis
Alpha Halogenation In Basic Conditions
Alpha Halogenation in Acidic Conditions
Haloform Reaction
*A methyl group is required for this reaction
O (^) 1. Acid (TFA)
R or H
X 2 (excess) NaOH (^) R or H O
When carbocations form, H’s and CH 3 ’s can do a 1,2-shift to generate a more stable carbocation intermediate
1,2-Hydride Shift
1,2-Methyl Shift
Hydrohalogenation
What’s added: H+ and Br- Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
Hydration
What’s added: H+^ and OH- Regioselectivity: Markovnikov Stereoselectivity : N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
Bromination in H 2 O
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
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 H 2 O attacks the more highly-substituted C:
In basic conditions, H 2 O attacks the less highly-substituted C:
Epoxidation
What’s added: O Regioselectivity: N/A Stereoselectivity : Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that a commonly-used peroxy acid is m -CPBA:
Catalytic Hydrogenation
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 Note: You may see Pt used as well. This is just the catalyst and does not change the outcome of the products.
Ozonolysis in Reducing Conditions
What’s added: 2 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
Do know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Note: (CH 3 ) 2 S is often abbreviated “DMS” for dimethyl sulfide.
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 KMnO 4. Unlike reducing conditions which would have formed aldehydes, oxidizing conditions produces carboxylic acids instead.
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
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
