Dat Bootcamp - Reaction Summary Sheet.pdf 4u6b3b
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Alkene Reactions
DAT Organic Chemistry Reaction Summary Sheet
Hydrohalogenation
Hydrohalogenation (with Rearrangement) Halogenation
Hydrobromination with Peroxide Hydration Hydration (with Rearrangement) Bromination in H2O
OxymercurationDemurcuration HydroborationOxidation Syn-Hydroxylation
Syn-Hydroxylation
Anti-Hydroxylation
Addition of an Alcohol Bromination in Alcohol
AlkoxymercurationDemurcuration Epoxidation
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Catalytic Hydrogenation
*Pt can also be used*
Ozonolysis (Reducing Conditions) Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage
1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
Alkyne Reactions Catalytic Hydrogenation (Catalytic Reduction) Reduction to CisAlkene Reduction to TransAlkene 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
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Ozonolysis/Oxidative Cleavage on an Internal Alkyne
1. O3 2. H2O2
O
O
or
OH
HO
1. KMnO4/heat 2. H3O+
Ozonolysis/Oxidative Cleavage on a Terminal Alkyne
1. O3 2. H2O2
O
or
CO2
OH
Terminal carbon becomes CO2
1. KMnO4/heat 2. H3O+
Free Radical Halogenation Reactions Free Radical Halogenation using Bromine (more selective) Free Radical Halogenation using Chlorine (less selective)
Br
Br2 hv or Δ Cl
Cl
Cl2
Cl
hv or Δ
Allylic/Benzylic Bromination
Cl NBS hv or Δ or ROOR
Br
NBS hv or Δ or ROOR
Br Br
Diels Alder Reactions Diene Addition to a Dienophile (Alkene)
hv or
Diene Addition to a Dienophile (Alkyne)
hv or
Diene Addition to a cis Dienophile
hv or same
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Diene Addition to a trans Dienophile
hv or enantiomers
Diene Addition to a substituted Dienophile
H
O
H O
H
hv or
endo (Major) O
H
H H
O
O exo (Minor)
H
H
Grignard Reactions Addition of a Grignard Reagent to an Aldehyde
O
Addition of a Grignard Reagent to a Ketone
O
1. H
OH
MgX , Ether
2. H3O+ 1.
2˚Alcohol
MgX , Ether
HO
3˚Alcohol
2. H3O+
Addition of a Grignard Reagent to an Ester
O
1. 2 eq. O
Addition of a Grignard Reagent to an Acyl Chloride
O
Addition of a Grignard Reagent to CO2
HO
MgX, Ether
HO
2. H3O+
3˚Alcohol O
MgX
1. CO2, Ether
OH
2. H3O+
Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side)
Addition of a Grignard Reagent to a Carboxylic Acid
3˚Alcohol
2. H3O+
1. 2 eq. Cl
MgX, Ether
O
1.
MgX , Ether
Carboxylic Acid
OH
2. H3O+
O
1. OH
MgX , Ether
2. H3O+
O O
MgX
Carboxylate
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Addition of a Grignard Reagent to an Amide
O NH2
O
MgX , Ether
1.
NH MgX
2. H3O+
Deprotonated Amide Addition of a Grignard Reagent to a Nitrile
1.
N
O
MgX , Ether
Ketone
2. H3O+
Electrophilic Aromatic Substitution (EAS) Reactions Friedel-Crafts Alkylation (Rearrangement Possible)
Cl AlCl3
Cl AlCl3
Friedel-Crafts Acylation (No Rearrangement Possible)
O
O
Cl AlCl3
Bromination Br2
Br
FeBr3
Chlorination Cl2
Cl
FeCl3
Nitration HNO3
NO2
H2SO4
Sulfonation
SO3 H2SO4
SO3H
H2SO4/Δ
Formylation
O CO, HCl
H
AlCl3
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EAS with an ortho/paradirecting group on Benzene
O/P
O/P
O/P Substituent
Substituent
Substituent
EAS with a meta-directing group on Benzene
M
M Substituent
Friedel-Crafts Alkylation/Acylation with a meta-directing group or an amine on Benzene
Substituent M
O R Cl
or Cl
R
No Reaction
AlCl3 NH2/NRH/NR2
O R Cl
or Cl
R
No Reaction
AlCl3
Benzene Side-Chain Reactions Side-Chain Oxidation of Benzene to form Benzoic Acid
R R
or
R
or
O
1. KMnO4, -OH 2. H3O+, Heat
OH
or Na2Cr2O7 H2SO4
1. KMnO4, -OH 2. H3O+, Heat or Na2Cr2O7
No Reaction (Requires free Hydrogen at Benzylic position)
H2SO4
Wolff-Kishner Reduction
O H2NNH2 or N2H4, -OH, Heat
Clemmensen Reduction
O Zn(Hg), HCl, Heat
NO2
Zn(Hg), HCl, Heat
NH2
*can also use H2/Pd, C in place of Zn(Hg), HCl, Heat for both reactions above
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Acetylation of Aniline using Acetic Anhydride
NH2
O
H N
O
O pyridine
Anilene
O Acetanilide
Hydride Reduction Reactions Reduction of an Aldehyde to a 1˚Alcohol
O
1. NaBH4, EtOH H
2. H3O+
O
1. LiAlH4, EtOH H
Reduction of a Ketone to a 2˚Alcohol
2. H3O+
O
1. NaBH4, EtOH
OH H OH H OH
2. H3O+ O
1. LiAlH4, EtOH
OH
2. H3O+
Reduction of a Carboxylic Acid to a 1˚Alcohol
O
Reduction of an Ester to a 1˚Alcohol
O
1. LiAlH4, EtOH OH
1. LiAlH4, EtOH O
Reduction of an Ester to an Aldehyde
O
O
O
OH
H
O H OH
2. H3O+
H
LiAlH[OC(CH3)3]3
O
Cl
Reduction of an Amide to an Amine
OH
2. H2O 1. LiAlH4, EtOH
Cl
Reduction of an Acyl Chloride to an Aldehyde
2. H3O+
H
1. DIBAL-H, -78°C O
Reduction of an Acyl Chloride to a 1˚Alcohol
2. H3O+
OH
H
O
1. LiAlH4, EtOH NH2
NH2 2. H3O+
Hoffmann Rearrangement
O
1. Br2 NH2
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2. NaOH
NH2
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Reduction of a Nitrile to an Amine
N
1. LiAlH4, EtOH
NH2
2. H3O+
Alcohol Reactions Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN1
Conversion of a 1˚/2˚Alcohol to an alkyl bromide via SN2
OH
HX
X
OH
HX
X
OH
PBr3
H
H OH
Conversion of a 1˚/2˚Alcohol to an alkyl chloride via SN2
SOCl2 H Pyridine
Conversion of an Alcohol to a Tosylate Ester (OTs)
OH
OH
Chromic Acid Oxidation of a 1o Alcohol to a Carboxylic Acid OH H
Br
PBr3
OH
OH
Acid-catalyzed Dehydration of an Alcohol
Br
Cl H Cl
SOCl2 Pyridine
OTs
TsCl
H3O+
Na2Cr2O7 or CrO3
Retention of Stereochemistry
Zaitsev’s Rule
O
H2SO4
OH
o
Chromic Acid Oxidation of a 2 Alcohol to a Ketone OH
Na2Cr2O7 or CrO3
O
H2SO4
Chromic Acid Oxidation of an Aldehyde to a Carboxylic Acid
Na2Cr2O7 or CrO3
O H
PCC or DMP Oxidation of a 1o Alcohol to an Aldehyde
OH H
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H2SO4 PCC or DMP
O OH O H
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PCC or DMP Oxidation of a 2o Alcohol to a Ketone Oxidative Cleavage of a 1,2 Diol
OH
HO
O
PCC or DMP OH
O
HIO4
O H
HO
OH
H
O
HIO4
O H
Ether and Epoxide Reactions Williamson Ether Synthesis via SN2 NaH, Na, or K OH
Acid-catalyzed Cleavage of Ethers when one side is 2˚/3˚ (Nucleophile attacks more substituted side via SN1)
O
Cl
O
HBr O
Br
HO
Br
HO
HBr O
Acid-catalyzed Cleavage of Ethers when neither side is 2˚/3˚ (Nucleophile attacks less substituted side via SN2)
O
Acid-catalyzed Ring Opening of Epoxides (Nucleophile attacks more substituted side)
Base-catalyzed Ring Opening of Epoxides (Nucleophile attacks less substituted side)
OH
HBr
Br
Cl
O
HCl
O
H3O+
O
OCH3
OH OH OH OH
HOCH3
O
Aldehyde and Ketone Reactions Nucleophilic Addition to an Aldehyde or Ketone
O
Addition of water to an Aldehyde or Ketone forming a Hydrate
O
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C or H
C or H
Nucleophile H3O+ H 2O H3O+ or -OH
HO
Nucleophile C or H
HO
OH C or H
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Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemi-acetal/Hemi-ketal
O
Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)
O
Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)
HO
O C or H
C or H
HO H3O+
C or H
O
O
O C or H
HO H3O+
O
OH
HO C or H
O
O C or H
H3O+ H3O+
Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+)
O
N
H 2N H3O+
C or H
C or H
H3O+
Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H3O+)
O C or H
N H H3O+
N C or H
H3O+
Double bond forms on more substituted end for Ketones Addition of a Wittig Reagent to an Aldehyde or Ketone
PPh3
O
C or H
C or H
Michael Addition to an α, β Unsaturated Ketone
O
O O
O or -CN, HNR2, HSR etc.
Michael Addition to an α, β Unsaturated Ketone with a Gilman Reagent (Organocuprates)
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O O
O
(CH3CH2CH2)2CuLi
O
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Carboxylic Acid Derivative Reactions Formation of an Acyl Chloride from a Carboxylic Acid via SOCl2
O
O
SOCl2
Cl
OH
Fischer Esterification
O
O
or
H3O+/CH3CH2OH
Cl
OH
O O
H3O+
Alpha Addition/Substitution Reactions Self Aldol Condensation and Enone Formation
O
-OH,
2
H
OH
O
-OH,
Δ O
H 2O
O
O
O
H3O+, NaOH
H
2
Mixed Aldol Condensation and Enone Formation
O
H 2O
-OH,
H
H O
OH H3O+, NaOH Δ OH
O
H 2O
H3O+, NaOH
O
Δ
O
O
O -OH,
O
H3O+, NaOH
H 2O
Δ HO
Self Claisen Condensation
O 2
Mixed Claisen Condensation
O
O
O
O
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O
O
O
2. H3O+
O
O
O
1. O
O
O
O
O
2. H3O+
O
Dieckmann Cyclization (Intramolecular Claisen Condensation) Acetoacetic Ester Synthesis
O
1. O
1. O 2. Cl 3. O 4. Cl 5. H3O+, Δ
O
1. O
O O
2. H3O+ O
CO2
HO
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Malonic Ester Synthesis
O O
O O
1. O 2. Cl 3. O 4. Cl 5. H3O+, Δ
O HO
CO2
2 HO
DAT Organic Chemistry Reaction Details Sheet Rearrangements Details
When carbocations form, H’s and CH3’s can do a 1,2-shift to generate a more stable carbocation intermediate 1,2-Hydride Shift
1,2-Methyl Shift
Alkene Reaction Details Hydrohalogenation
What’s added: H+ and BrRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
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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:
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Hydration
What’s added: H+ and OHRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
Bromination in H2O
What’s added: Br+ and OHRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:
Oxymercuration-Demercuration
What’s added: H+ and OHRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion bridge Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
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Hydroboration-Oxidation
What’s added: H+ and OHRegioselectivity: Anti-Markovnikov Stereoselectivity: Syn Intermediate: Hydroxy-boranes Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
Syn-Hydroxylation
or What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism:
Anti-Hydroxylation
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:
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Addition of an Alcohol
What’s added: H+ and ORRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible Mechanism:
Bromination in Alcohol
What’s added: Br+ and ORRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:
Alkoxymercuration-Demercuration
What’s added: H+ and OCH3Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
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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-BA:
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: (CH3)2S is often abbreviated “DMS” for dimethyl sulfide.
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Ozonolysis in Oxidizing Conditions/Oxidative Cleavage 1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
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 1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
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. 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.
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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
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 Reduction to Trans-Alkene
What’s added: 2 H 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
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: Possible Mechanism: The halogen goes to the C with fewer H’s
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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: Possible Mechanism: Same as for terminal alkynes, but yields a mixture of two products because both intermediates are equally stable
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.
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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.
Hydration of a Terminal Alkyne (Anti-Markovnikov)
What’s added: 1 O atom Regioselectivity: Anti-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 Anti-Markovnikov enols, which then tautomerize to form aldehydes.
SN2 Addition of an Acetylide Ion to an Alkyl Halide
What’s added: additional C atoms (-R of alkyl halide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then alkylation via SN2 reaction
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SN2 Addition of an Acetylide Ion to a Ketone
What’s added: 2 additional alkyl groups and 1 –OH group Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of a ketone via SN2 reaction
SN2 Addition of an Acetylide Ion to an Epoxide
What’s added: 2-hydroxylpropane (from epoxide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of 2-hydroxyl propane via SN2 reaction
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Ozonolysis/Oxidative Cleavage on an Internal Alkyne 1. O3 2. H2O2
O
or
O OH
HO
1. KMnO4/heat 2. H3O+
What’s added: 4 O atoms and 2 H atoms 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 a triple bond in half, very similar to ozonolysis on an alkene. An O replaces two of the bonds as C=O and the third lone bond becomes a bond to -OH. Unlike ozonolysis, instead of forming the C-H bond of an aldehyde, a C-OH bond of a carboxylic acid is formed. 1. O3 2. H2O2
O
or
O OH
HO
1. KMnO4/heat 2. H3O+
Ozonolysis/Oxidative Cleavage on a Terminal Alkyne 1. O3 2. H2O2
O
or
OH
CO2 Terminal carbon becomes CO2
1. KMnO4/heat 2. H3O+
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 a triple bond in half, very similar to ozonolysis on an alkene. 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+
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O OH
CO2 Terminal carbon becomes CO2
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Free Radical Halogenation Reaction Details Free Radical Halogenation using Bromine (more selective) Br
Br2 hv or Δ
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 ing to create an alkyl halide 1. Initiation
Br Br
hv or Δ
Br
Br
2. Propagation H Br
HBr
Br Br Br
Br alkyl halide
3. Termination Br
Br
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Br Br
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Free Radical Halogenation using Chlorine (less selective) Cl Cl
Cl2
Cl
hv or Δ
Cl What’s added: 1 Cl atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Radical Intermediate Rearrangement: Not possible Mechanism: Formation of chlorine and carbon radicals and them ing to create alkyl halides
1. Initiation hv or Δ
Cl Cl
Cl
Cl
2. Propagation H
H
Cl
Cl
HCl
HCl
Cl
Cl
Cl Cl
Cl
Cl Cl
Cl
alkyl halide
Cl
alkyl halide
H
Cl
HCl
HCl H
Cl Cl
Cl
Cl
Cl Cl
Cl
alkyl halide
Cl alkyl halide
3. Termination Cl
Cl
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Cl Cl
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Allylic/Benzylic Bromination NBS hv or Δ or ROOR
Br
NBS hv or Δ or ROOR
Br Br
What’s added: 1 Br atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Allylic Radical Intermediate Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Note: this reaction results in the formation of allylic radical intermediates which resonate and thus allow for the formation of multiple products. Br
Br NBS hv or Δ or ROOR
allylic radical intermediates Br Br
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Grignard Reaction Details Addition of a Grignard Reagent to an Aldehyde/Ketone O
1. H
O
OH
MgX , Ether
2º Alcohol
2. H3O+ 1.
MgX , Ether
HO 3º Alcohol
2. H3O+
What’s added: R group Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Alkoxide ion Rearrangement: N/A Mechanism: Grignard reagents are electron-rich and attack electrophilic species such as carbonyls. The mechanism follows typical nucleophilic addition to a carbonyl, forming 2º or 3º Alcohols.
O
1.
O
MgX , Ether
C or H 2. H3O+
O C or H
C or H alkoxide intermediate
H3
O+
HO C or H
2º or 3º Alcohol
Note: Using R-MgX is virtually the same reaction as using R-Li (organolithium); you are using the R-group as a nucleophile to form an alcohol. Addition of a Grignard Reagent to an Ester/Acyl Chloride O
1. 2 eq. O
O
HO
2. H3O+
1. 2 eq. Cl
MgX, Ether
2. H3
MgX, Ether
HO
O+
What’s added: 2 R groups Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Tetrahedral intermediate Rearrangement: N/A
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Mechanism: Grignard reagents are electron-rich and attack electrophilic species such as carbonyls. The mechanism follows typical nucleophilic addition to a carbonyl with a twist; the Grignard reagent adds twice with esters and acyl chlorides, forming 3º alcohols. Here it is shown on an ester (the same mechanism as with an acyl chloride): O
1. 2 eq. O
O
MgX, Ether
O O
2. H3O+
O tetrahedral intermediate
O
H3O+
O
HO 3º Alcohol
Carboxylic Acid Derivative Reaction Details Fischer Esterification O
or
O Cl
OH
O
H3O+/CH3CH2OH
O
H3O+
What’s added: An alcohol Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Tetrahedral intermediate Rearrangement: N/A Mechanism: Essentially, this reaction substitutes the Cl or OH of an acyl chloride/ester with an alcohol:
O
H3O+/CH3CH2OH OH
O
OH
OH
H-OH2 OH
OH
OH
HO
H 2O
HO
O H OH
HO
O OH2
O
H O
O
H3O+ O
tetrahedral intermediate
Notes: Notice that the reaction is reversible under H3O+/heat. The reverse reaction is how esters are cleaved into their corresponding carboxylic acid and alcohol, an important biological process.
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DAT Organic Chemistry Reaction Summary Sheet
Hydrohalogenation
Hydrohalogenation (with Rearrangement) Halogenation
Hydrobromination with Peroxide Hydration Hydration (with Rearrangement) Bromination in H2O
OxymercurationDemurcuration HydroborationOxidation Syn-Hydroxylation
Syn-Hydroxylation
Anti-Hydroxylation
Addition of an Alcohol Bromination in Alcohol
AlkoxymercurationDemurcuration Epoxidation
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Catalytic Hydrogenation
*Pt can also be used*
Ozonolysis (Reducing Conditions) Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage
1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
Alkyne Reactions Catalytic Hydrogenation (Catalytic Reduction) Reduction to CisAlkene Reduction to TransAlkene 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
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Ozonolysis/Oxidative Cleavage on an Internal Alkyne
1. O3 2. H2O2
O
O
or
OH
HO
1. KMnO4/heat 2. H3O+
Ozonolysis/Oxidative Cleavage on a Terminal Alkyne
1. O3 2. H2O2
O
or
CO2
OH
Terminal carbon becomes CO2
1. KMnO4/heat 2. H3O+
Free Radical Halogenation Reactions Free Radical Halogenation using Bromine (more selective) Free Radical Halogenation using Chlorine (less selective)
Br
Br2 hv or Δ Cl
Cl
Cl2
Cl
hv or Δ
Allylic/Benzylic Bromination
Cl NBS hv or Δ or ROOR
Br
NBS hv or Δ or ROOR
Br Br
Diels Alder Reactions Diene Addition to a Dienophile (Alkene)
hv or
Diene Addition to a Dienophile (Alkyne)
hv or
Diene Addition to a cis Dienophile
hv or same
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Diene Addition to a trans Dienophile
hv or enantiomers
Diene Addition to a substituted Dienophile
H
O
H O
H
hv or
endo (Major) O
H
H H
O
O exo (Minor)
H
H
Grignard Reactions Addition of a Grignard Reagent to an Aldehyde
O
Addition of a Grignard Reagent to a Ketone
O
1. H
OH
MgX , Ether
2. H3O+ 1.
2˚Alcohol
MgX , Ether
HO
3˚Alcohol
2. H3O+
Addition of a Grignard Reagent to an Ester
O
1. 2 eq. O
Addition of a Grignard Reagent to an Acyl Chloride
O
Addition of a Grignard Reagent to CO2
HO
MgX, Ether
HO
2. H3O+
3˚Alcohol O
MgX
1. CO2, Ether
OH
2. H3O+
Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side)
Addition of a Grignard Reagent to a Carboxylic Acid
3˚Alcohol
2. H3O+
1. 2 eq. Cl
MgX, Ether
O
1.
MgX , Ether
Carboxylic Acid
OH
2. H3O+
O
1. OH
MgX , Ether
2. H3O+
O O
MgX
Carboxylate
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Addition of a Grignard Reagent to an Amide
O NH2
O
MgX , Ether
1.
NH MgX
2. H3O+
Deprotonated Amide Addition of a Grignard Reagent to a Nitrile
1.
N
O
MgX , Ether
Ketone
2. H3O+
Electrophilic Aromatic Substitution (EAS) Reactions Friedel-Crafts Alkylation (Rearrangement Possible)
Cl AlCl3
Cl AlCl3
Friedel-Crafts Acylation (No Rearrangement Possible)
O
O
Cl AlCl3
Bromination Br2
Br
FeBr3
Chlorination Cl2
Cl
FeCl3
Nitration HNO3
NO2
H2SO4
Sulfonation
SO3 H2SO4
SO3H
H2SO4/Δ
Formylation
O CO, HCl
H
AlCl3
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EAS with an ortho/paradirecting group on Benzene
O/P
O/P
O/P Substituent
Substituent
Substituent
EAS with a meta-directing group on Benzene
M
M Substituent
Friedel-Crafts Alkylation/Acylation with a meta-directing group or an amine on Benzene
Substituent M
O R Cl
or Cl
R
No Reaction
AlCl3 NH2/NRH/NR2
O R Cl
or Cl
R
No Reaction
AlCl3
Benzene Side-Chain Reactions Side-Chain Oxidation of Benzene to form Benzoic Acid
R R
or
R
or
O
1. KMnO4, -OH 2. H3O+, Heat
OH
or Na2Cr2O7 H2SO4
1. KMnO4, -OH 2. H3O+, Heat or Na2Cr2O7
No Reaction (Requires free Hydrogen at Benzylic position)
H2SO4
Wolff-Kishner Reduction
O H2NNH2 or N2H4, -OH, Heat
Clemmensen Reduction
O Zn(Hg), HCl, Heat
NO2
Zn(Hg), HCl, Heat
NH2
*can also use H2/Pd, C in place of Zn(Hg), HCl, Heat for both reactions above
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Acetylation of Aniline using Acetic Anhydride
NH2
O
H N
O
O pyridine
Anilene
O Acetanilide
Hydride Reduction Reactions Reduction of an Aldehyde to a 1˚Alcohol
O
1. NaBH4, EtOH H
2. H3O+
O
1. LiAlH4, EtOH H
Reduction of a Ketone to a 2˚Alcohol
2. H3O+
O
1. NaBH4, EtOH
OH H OH H OH
2. H3O+ O
1. LiAlH4, EtOH
OH
2. H3O+
Reduction of a Carboxylic Acid to a 1˚Alcohol
O
Reduction of an Ester to a 1˚Alcohol
O
1. LiAlH4, EtOH OH
1. LiAlH4, EtOH O
Reduction of an Ester to an Aldehyde
O
O
O
OH
H
O H OH
2. H3O+
H
LiAlH[OC(CH3)3]3
O
Cl
Reduction of an Amide to an Amine
OH
2. H2O 1. LiAlH4, EtOH
Cl
Reduction of an Acyl Chloride to an Aldehyde
2. H3O+
H
1. DIBAL-H, -78°C O
Reduction of an Acyl Chloride to a 1˚Alcohol
2. H3O+
OH
H
O
1. LiAlH4, EtOH NH2
NH2 2. H3O+
Hoffmann Rearrangement
O
1. Br2 NH2
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2. NaOH
NH2
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Reduction of a Nitrile to an Amine
N
1. LiAlH4, EtOH
NH2
2. H3O+
Alcohol Reactions Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN1
Conversion of a 1˚/2˚Alcohol to an alkyl bromide via SN2
OH
HX
X
OH
HX
X
OH
PBr3
H
H OH
Conversion of a 1˚/2˚Alcohol to an alkyl chloride via SN2
SOCl2 H Pyridine
Conversion of an Alcohol to a Tosylate Ester (OTs)
OH
OH
Chromic Acid Oxidation of a 1o Alcohol to a Carboxylic Acid OH H
Br
PBr3
OH
OH
Acid-catalyzed Dehydration of an Alcohol
Br
Cl H Cl
SOCl2 Pyridine
OTs
TsCl
H3O+
Na2Cr2O7 or CrO3
Retention of Stereochemistry
Zaitsev’s Rule
O
H2SO4
OH
o
Chromic Acid Oxidation of a 2 Alcohol to a Ketone OH
Na2Cr2O7 or CrO3
O
H2SO4
Chromic Acid Oxidation of an Aldehyde to a Carboxylic Acid
Na2Cr2O7 or CrO3
O H
PCC or DMP Oxidation of a 1o Alcohol to an Aldehyde
OH H
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H2SO4 PCC or DMP
O OH O H
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PCC or DMP Oxidation of a 2o Alcohol to a Ketone Oxidative Cleavage of a 1,2 Diol
OH
HO
O
PCC or DMP OH
O
HIO4
O H
HO
OH
H
O
HIO4
O H
Ether and Epoxide Reactions Williamson Ether Synthesis via SN2 NaH, Na, or K OH
Acid-catalyzed Cleavage of Ethers when one side is 2˚/3˚ (Nucleophile attacks more substituted side via SN1)
O
Cl
O
HBr O
Br
HO
Br
HO
HBr O
Acid-catalyzed Cleavage of Ethers when neither side is 2˚/3˚ (Nucleophile attacks less substituted side via SN2)
O
Acid-catalyzed Ring Opening of Epoxides (Nucleophile attacks more substituted side)
Base-catalyzed Ring Opening of Epoxides (Nucleophile attacks less substituted side)
OH
HBr
Br
Cl
O
HCl
O
H3O+
O
OCH3
OH OH OH OH
HOCH3
O
Aldehyde and Ketone Reactions Nucleophilic Addition to an Aldehyde or Ketone
O
Addition of water to an Aldehyde or Ketone forming a Hydrate
O
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C or H
C or H
Nucleophile H3O+ H 2O H3O+ or -OH
HO
Nucleophile C or H
HO
OH C or H
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Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemi-acetal/Hemi-ketal
O
Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)
O
Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)
HO
O C or H
C or H
HO H3O+
C or H
O
O
O C or H
HO H3O+
O
OH
HO C or H
O
O C or H
H3O+ H3O+
Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+)
O
N
H 2N H3O+
C or H
C or H
H3O+
Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H3O+)
O C or H
N H H3O+
N C or H
H3O+
Double bond forms on more substituted end for Ketones Addition of a Wittig Reagent to an Aldehyde or Ketone
PPh3
O
C or H
C or H
Michael Addition to an α, β Unsaturated Ketone
O
O O
O or -CN, HNR2, HSR etc.
Michael Addition to an α, β Unsaturated Ketone with a Gilman Reagent (Organocuprates)
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O O
O
(CH3CH2CH2)2CuLi
O
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Carboxylic Acid Derivative Reactions Formation of an Acyl Chloride from a Carboxylic Acid via SOCl2
O
O
SOCl2
Cl
OH
Fischer Esterification
O
O
or
H3O+/CH3CH2OH
Cl
OH
O O
H3O+
Alpha Addition/Substitution Reactions Self Aldol Condensation and Enone Formation
O
-OH,
2
H
OH
O
-OH,
Δ O
H 2O
O
O
O
H3O+, NaOH
H
2
Mixed Aldol Condensation and Enone Formation
O
H 2O
-OH,
H
H O
OH H3O+, NaOH Δ OH
O
H 2O
H3O+, NaOH
O
Δ
O
O
O -OH,
O
H3O+, NaOH
H 2O
Δ HO
Self Claisen Condensation
O 2
Mixed Claisen Condensation
O
O
O
O
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O
O
O
2. H3O+
O
O
O
1. O
O
O
O
O
2. H3O+
O
Dieckmann Cyclization (Intramolecular Claisen Condensation) Acetoacetic Ester Synthesis
O
1. O
1. O 2. Cl 3. O 4. Cl 5. H3O+, Δ
O
1. O
O O
2. H3O+ O
CO2
HO
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Malonic Ester Synthesis
O O
O O
1. O 2. Cl 3. O 4. Cl 5. H3O+, Δ
O HO
CO2
2 HO
DAT Organic Chemistry Reaction Details Sheet Rearrangements Details
When carbocations form, H’s and CH3’s can do a 1,2-shift to generate a more stable carbocation intermediate 1,2-Hydride Shift
1,2-Methyl Shift
Alkene Reaction Details Hydrohalogenation
What’s added: H+ and BrRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
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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:
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Hydration
What’s added: H+ and OHRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:
Bromination in H2O
What’s added: Br+ and OHRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:
Oxymercuration-Demercuration
What’s added: H+ and OHRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion bridge Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
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Hydroboration-Oxidation
What’s added: H+ and OHRegioselectivity: Anti-Markovnikov Stereoselectivity: Syn Intermediate: Hydroxy-boranes Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
Syn-Hydroxylation
or What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism:
Anti-Hydroxylation
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:
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Addition of an Alcohol
What’s added: H+ and ORRegioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible Mechanism:
Bromination in Alcohol
What’s added: Br+ and ORRegioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:
Alkoxymercuration-Demercuration
What’s added: H+ and OCH3Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction
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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-BA:
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: (CH3)2S is often abbreviated “DMS” for dimethyl sulfide.
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Ozonolysis in Oxidizing Conditions/Oxidative Cleavage 1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
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 1. O3 2. H2O2 or
O O
OH
1. KMnO4/heat 2. H3O+
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. 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.
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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
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 Reduction to Trans-Alkene
What’s added: 2 H 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
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: Possible Mechanism: The halogen goes to the C with fewer H’s
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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: Possible Mechanism: Same as for terminal alkynes, but yields a mixture of two products because both intermediates are equally stable
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.
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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.
Hydration of a Terminal Alkyne (Anti-Markovnikov)
What’s added: 1 O atom Regioselectivity: Anti-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 Anti-Markovnikov enols, which then tautomerize to form aldehydes.
SN2 Addition of an Acetylide Ion to an Alkyl Halide
What’s added: additional C atoms (-R of alkyl halide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then alkylation via SN2 reaction
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SN2 Addition of an Acetylide Ion to a Ketone
What’s added: 2 additional alkyl groups and 1 –OH group Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of a ketone via SN2 reaction
SN2 Addition of an Acetylide Ion to an Epoxide
What’s added: 2-hydroxylpropane (from epoxide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of 2-hydroxyl propane via SN2 reaction
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Ozonolysis/Oxidative Cleavage on an Internal Alkyne 1. O3 2. H2O2
O
or
O OH
HO
1. KMnO4/heat 2. H3O+
What’s added: 4 O atoms and 2 H atoms 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 a triple bond in half, very similar to ozonolysis on an alkene. An O replaces two of the bonds as C=O and the third lone bond becomes a bond to -OH. Unlike ozonolysis, instead of forming the C-H bond of an aldehyde, a C-OH bond of a carboxylic acid is formed. 1. O3 2. H2O2
O
or
O OH
HO
1. KMnO4/heat 2. H3O+
Ozonolysis/Oxidative Cleavage on a Terminal Alkyne 1. O3 2. H2O2
O
or
OH
CO2 Terminal carbon becomes CO2
1. KMnO4/heat 2. H3O+
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 a triple bond in half, very similar to ozonolysis on an alkene. 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+
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O OH
CO2 Terminal carbon becomes CO2
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Free Radical Halogenation Reaction Details Free Radical Halogenation using Bromine (more selective) Br
Br2 hv or Δ
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 ing to create an alkyl halide 1. Initiation
Br Br
hv or Δ
Br
Br
2. Propagation H Br
HBr
Br Br Br
Br alkyl halide
3. Termination Br
Br
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Br Br
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Free Radical Halogenation using Chlorine (less selective) Cl Cl
Cl2
Cl
hv or Δ
Cl What’s added: 1 Cl atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Radical Intermediate Rearrangement: Not possible Mechanism: Formation of chlorine and carbon radicals and them ing to create alkyl halides
1. Initiation hv or Δ
Cl Cl
Cl
Cl
2. Propagation H
H
Cl
Cl
HCl
HCl
Cl
Cl
Cl Cl
Cl
Cl Cl
Cl
alkyl halide
Cl
alkyl halide
H
Cl
HCl
HCl H
Cl Cl
Cl
Cl
Cl Cl
Cl
alkyl halide
Cl alkyl halide
3. Termination Cl
Cl
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Cl Cl
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Allylic/Benzylic Bromination NBS hv or Δ or ROOR
Br
NBS hv or Δ or ROOR
Br Br
What’s added: 1 Br atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Allylic Radical Intermediate Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Note: this reaction results in the formation of allylic radical intermediates which resonate and thus allow for the formation of multiple products. Br
Br NBS hv or Δ or ROOR
allylic radical intermediates Br Br
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Grignard Reaction Details Addition of a Grignard Reagent to an Aldehyde/Ketone O
1. H
O
OH
MgX , Ether
2º Alcohol
2. H3O+ 1.
MgX , Ether
HO 3º Alcohol
2. H3O+
What’s added: R group Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Alkoxide ion Rearrangement: N/A Mechanism: Grignard reagents are electron-rich and attack electrophilic species such as carbonyls. The mechanism follows typical nucleophilic addition to a carbonyl, forming 2º or 3º Alcohols.
O
1.
O
MgX , Ether
C or H 2. H3O+
O C or H
C or H alkoxide intermediate
H3
O+
HO C or H
2º or 3º Alcohol
Note: Using R-MgX is virtually the same reaction as using R-Li (organolithium); you are using the R-group as a nucleophile to form an alcohol. Addition of a Grignard Reagent to an Ester/Acyl Chloride O
1. 2 eq. O
O
HO
2. H3O+
1. 2 eq. Cl
MgX, Ether
2. H3
MgX, Ether
HO
O+
What’s added: 2 R groups Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Tetrahedral intermediate Rearrangement: N/A
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Mechanism: Grignard reagents are electron-rich and attack electrophilic species such as carbonyls. The mechanism follows typical nucleophilic addition to a carbonyl with a twist; the Grignard reagent adds twice with esters and acyl chlorides, forming 3º alcohols. Here it is shown on an ester (the same mechanism as with an acyl chloride): O
1. 2 eq. O
O
MgX, Ether
O O
2. H3O+
O tetrahedral intermediate
O
H3O+
O
HO 3º Alcohol
Carboxylic Acid Derivative Reaction Details Fischer Esterification O
or
O Cl
OH
O
H3O+/CH3CH2OH
O
H3O+
What’s added: An alcohol Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Tetrahedral intermediate Rearrangement: N/A Mechanism: Essentially, this reaction substitutes the Cl or OH of an acyl chloride/ester with an alcohol:
O
H3O+/CH3CH2OH OH
O
OH
OH
H-OH2 OH
OH
OH
HO
H 2O
HO
O H OH
HO
O OH2
O
H O
O
H3O+ O
tetrahedral intermediate
Notes: Notice that the reaction is reversible under H3O+/heat. The reverse reaction is how esters are cleaved into their corresponding carboxylic acid and alcohol, an important biological process.
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