-
8/13/2019 Reaction_Summary Organic Chemistry
1/5
Reaction Summary
R
Nucleophilic substitution: alkyl-leaving
group!alkyl-nucleophile
LGNucleophile
Aprotic polarsolvent
Nu LGNucleophile
Proticsolvent
Nu
Via carbocation intermediate (SN1)Concerted reaction (SN2)
Elimination: alkyl-leaving group!alkene
LGStrong base
OH
Via carbocation intermediate (E1)Concerted reaction (E2)
H2SO4
heat heat
Halogen addition:alkene!
vicinal dihaloalkane or halohydrin
Br2Br
Br
Anti addition(cyclicbromoniumion)CH2Cl2H2O
Br2OH
Br
ROH addition: alkene!alcohol or etherO Markovnikov
addition(no stereochemconstraints)H2O
OH H2SO4
Via carbocation intermediate
H2SO4
ROH
ROxymercuration/reduction: alkene!alcohol or ether
O Markovnikovaddition(Antiaddition)
OH 1. Hg(OAc)2/ H2O
2. NaBH4
1. Hg(OAc)2/ ROH
2. NaBH4
Hydroboration/oxidation:
alkene!alcoholAnti-Markovnikovaddition(Synaddition)
1. BH3
2. NaOH/H2O2
OH
Ozonolysis: alkene!carboxylic acids or aldehydes
O
OH 1. O3
2. H2O2O H
OH 1. O3
2. (CH3)2SO
H
O H
H
-
8/13/2019 Reaction_Summary Organic Chemistry
2/5
OH
Tosylate synthesis: alcohol !tosylateCH3S
O
O
Cl
Pyridine
Tosyl chloride(TsCl)
O S
O
O
CH3
R-OTs
OH
Alkyl halide synthesis: alcohol !alkyl halidePBr3 SOCl2
Pyridine
Br Cl
OH
Alcohol oxidation: alcohol !aldehydeCrO3
Pyridine H
O(PCC)
OH
Alcohol oxidation: alcohol !carboxylic acid or ketone
OH
OK2Cr2O7 OH OK2Cr2O7
OHHO
Glycol oxidation: glycol!aldehyde and/or ketoneH5IO6 O HO
Nucleophilic substitution: alkyl-leaving group!alcohol
LG
Aprotic polarsolvent
Concerted reaction (SN2)
O
O
CH3
O
O
CH3
NaOH/H2O
OH
For secondarysubstrates
-
8/13/2019 Reaction_Summary Organic Chemistry
3/5
Hydrogenation: alkene!alkaneH2
Pd/C
Hydrogenation: alkyne!alkaneH2
Pd/C
Hydrogenation: alkyne!alkeneH2
Lindlar
Na
NH3
Hydrogenation: aromatic !aromatic or to alkaneH2
Pt, high pressure
H2
Pd/C
trans cis
OsO4
H2O/t-butyl alcoholpyridine/TMAO
Glycol synthesis: alkene!glycolOHHO
Synaddition
Epoxide synthesis: alkene!epoxide
Synaddition
ClO
O
OH
m-chloro-peroxy-benzoicacid(MCPBA)
O
Epoxide synthesis: halohydrin!epoxide
OH
O
Br NaOH (1 equiv)
SN2 attack by hydroxyl
on carbon with Br
-
8/13/2019 Reaction_Summary Organic Chemistry
4/5
Epoxide ring-opening (basic): epoxide!alcohol and nucleophileO
1. Nucleophile (basic conditions)
2. Protonate product
OH
Nu
(Example:if the nucleophile is
an alcoxide (RO), the result
is an alcohol/ether; note that
the nucleophile is on the
less substituted carbon.)
Epoxide ring-opening (acidic): epoxide!alcohol and nucleophileO
Nucleophile
H2SO4
Nu
OH
(Example:if the nucleophile isan alcohol, the resultis an
alcohol/ether); note thatthe nucleophile is on themore substituted
carbon.)
Epoxide ring-opening (Grignard) epoxide!alcohol two carbons
longerO
R
Note: this only yieldspredictable product
when using oxirane)Oxirane
1. R-Mg-Br
2. Protonate product
OH
HX addition: alkyne!vinyl halideHBr
Br
Note: excess HBr willresult ingeminal dibromidefollowing second
HBr addition
Hydration: alkyne!ketoneO Markovnikov addition
followed by enol/ketotautomerization
Hg2+/H2O
Hydroboration/oxidation: alkyne!aldehyde
Anti-Markovnikovaddition(Synaddition)followed
byenol/ketotautomerization
1. BH(amyl)2
2. NaOH/H2O2
O
H
Grignard synthesis: alkyne!Grignard reagentCH3CH2MgBr
etherMgBr
Grignard synthesis: haloalkane!Grignard reagentBrR
Mg
etherR MgBr
-
8/13/2019 Reaction_Summary Organic Chemistry
5/5
R
R
HNO3
H2SO4
EAS Nitration: aromatic!nitro-aromaticNO2
X2
FeX3 (X= Cl, Br, I)
EAS Halogenation: aromatic!halo-aromaticX
R-Cl
AlCl3
Friedel-Crafts Alkylation: aromatic!alkyl-aromaticR
+ others
Friedel-Crafts Acylation: aromatic!acyl-aromatic
AlCl3
R Cl
O
+ others RR
H2SO4
SO3
H2SO4
EAS Sulfonation: aromatic!aromatic sulfonic acidSO3H
Benzylic/allylic bromination
CH2
Benzylic oxidation: alkyl-aromatic!aromatic carboxylic acid
NO O
BrNBS
R OH
O
Br
CH3
R
O
KMnO4
Nucleophilic aromatic substitution: aryl
halide!aryl-nucleophileX
A
Nucleophile Nu
A
Note: at leastone activating group in
ortho orpara position isnecessry
