Roadmap

TG ~ @bohring_bot × @HeyitsyashXD
The
organic chemistry
Reagent
Book
Index Index
4 5
Index Index
Reagents and Solvents End Notes
Ac2O Acetic Anhydride 6 HgSO4 Mercuric Sulfate 54 NMO N–methylmorpholine Common Abbreviations & Terms 134
AgNO3 Silver Nitrate 7 HI Hydroiodic acid 55 Functional Groups 135
Ag2O Silver Oxide 8 HIO4 Periodic acid 57 O3 pKas of Common Functional Groups
) 58 R2CuLi Organocuprates 104 136
2
propionitrile)] 9 HNO3 Nitric Acid 59 RLi Organolithium reagents 105 Notes on Acids 138
AlBr3 Aluminum bromide 10 H2O2 Hydrogen peroxide 60 OsO4 Osmium tetroxide 108 Notes on Bases 140
AlCl3 Aluminum chloride 11 H3PO4 Phosphoric acid 62 4
Lead tetraacetate 109
BF3 H2SO4 Sulfuric acid 63 PBr3 Phosphorus tribromide 110 Reducing Agents 143
BH3 Borane 14 I2 Iodine 64 PCl3 Phosphorus trichloride 111 Organometallic Reagents 145
Br2 Bromine 16 KMnO4 Potassium permanganate 66 PCl5 Phosphorus Pentachloride 112 Reagents for Making Alkyl/Acyl
BsCl p KCN Potassium cyanide 23 P2O5 Phosphorus pentoxide 113 Halides 147
sulfonyl chloride 19 KOt t Pd/C Palladium on carbon 114 Reagents Involving Aromatic Rings
CCl4 Carbon Tetrachloride 151 KPhth Potassium Phthalimide 70 ) Palladium “tetrakis”
3 4
155 148
CH2Cl2 Dichloromethane 151 LDA Lithium diisopropyl amide 71 Pt Platinum 115 Types of Arrows 150
Cl2 Chlorine 20 Li Lithium 72 PCC Pyridinium chlorochromate 116 Types of Solvents 151
CN Cyanide ion 23 POCl3 Phosphorus oxychloride 117 Protecting Groups 152
CrO3 Chromium trioxide 24 LiAlH4 Lithium aluminum hydride 75 PPh3 Triphenylphosphine 118
t-Bu)3 Pyridine 119 Cross Coupling Reagents 155
aluminum hydride 77 Ra–Ni Raney Nickel 120
m m-chloroperoxy RO–OR Peroxides 121
D Deuterium 32 SO3 Sulfur trioxide 122
Mg Magnesium 80 SOBr2 Thionyl bromide 123
MsCl Methanesulfonyl chloride 81 SOCl2 Thionyl chloride 124
DCC N,N NaN3 Sn Tin 125
carbodiimide 29 Na Sodium 83 TBAF Tetrabutyl ammonium
CH2N2 NaBH4 Sodium borohydride 85
Sodium triacetoxy THF Tetrahydrofuran 151
3
hydride 33 borohydride 87 TMSCl Trimethylsilyl chloride 127
NaCNBH3 Sodium TsCl p
cyanoborohydride 88 chloride 128
Na2Cr2O7 Sodium dichromate 50 TsOH p
DMSO Dimethyl sulfoxide 151 NaH Sodium Hydride 89 Zn Zinc 130
Et2O Diethyl ether 151 NaIO4 Sodium periodate 90
Fe Iron 36 NaNO2 Sodium nitrite 58
FeBr3 NaNH2 Sodium amide 91 Odds And Ends 133
FeCl3 NaOH Sodium hydroxide 92
Grignard Reagents 40 NaOEt Sodium Ethoxide 93
NBS N–Bromosuccinimide 94
H2 Hydrogen 43 NCS N–Chloro Succinimide 96
H+ Anhydrous Acid 44 NIS N–Iodo Succinimide 97
H3O+ Aqueous acid 45 NH2OH Hydroxylamine 98
HBr Hydrobromic acid 46 NH3 Ammonia 99
HCl Hydrochloric acid 48 NH2NH2
H2CrO4 Chromic acid 50 Ni2B Nickel boride 101
2
Mercuric Acetate 52
Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index
Index Index
6 7
Ac2O 3
Acetic Anhydride
Similar to: 4
N
1) conversion of alkyl halides to alcohols
Example 1: Acetylation of alcohols
N
1) conversion of alkyl halides to ethers
Example 2: Conversion of carboxylic acids to anhydrides
How it works: SN1 Reaction of alkyl halides
Many other catalysts

besides AlCl3 can be used
(e.g. BF3, FeCl3)
How it works: Friedel-Crafts Acylation
Activation of Ac2O Acylium ion

with Lewis acid (reactive intermediate)
Attack of aromatic ring on Re-aromatization (often shown

acylium ion electrophile with generic base B– )
Tdorf
Index Index
8 9
Ag2O
Similar to: 3 Similar to:

Example 1: Tollens oxidation of aldehydes to carboxylic acids
How it works: Free-radical halogenation of alkenes

This reaction is usually
introduced in the con-
text of sugar chemistry
Example 2: As the base in the Hoffmann elimination

f
10
3
Index
I
Index
3
11
Also known as: Also known as:
Similar to: 3 3 3
Similar to: 3 3 3
alcohols to aldehydes
How it works: Friedel-Crafts acylation

Index Index
12 13
3
BF3
How it works: Meerwein-Ponndorf-Verley Oxidation

-
-
3 Similar to: 3 3
Example 1: Conversion of ketones to thioacetals
How it works: Formation of thioacetals

3
Coordination Addition
Proton transfer
Addition
Elimination
This is the key step. Note how the
ketone is reduced to a secondary
alcohol and the alcohol is oxidized.
Deprotonation
The aluminum alkoxide can go on to

catalyze further reactions.

Index Index
14 15
BH3 BH3
Borane
Similar to: 6 3 3
How it works: Hydroboration of alkenes How it works: Hydroboration of alkynes

boron adds to the less substituted end of enol
the alkene tautomerism
keto -
hydrogen has a partial negative charge and the boron has a partial positive
the partially negative
hydrogen “lines up” with the more substituted end of the double bond
syn

Index Index
16 17
Br2 Br2
Bromine
Similar to: acids
How it works: Bromination of alkenes
Example 3: Conversion of alkenes to halohydrins
How it works: Bromination of alkenes
Example 6: Conversion of ketones to
Example 7: Conversion of enolates to

Index Index
18 19
Br2
p
How it works: Hoffmann Rearrangement
In this reaction, the lone pair on nitrogen attacks bromine, which leads to a re- Also known as:
arrangement. Attack at the carbonyl carbon by water then leads to loss of CO2,
resulting in the formation of the free amine. p
Similar to:
Example 1: Conversion of alcohols into alkyl brosylates
Attack
Bromination Rearrangement by H2O
Loss of CO2
How it works: Bromination of enols
How it works: Bromination of enolates
How it works: Halogenation of alkanes

Index Index
20 21
2 2
Example 8: The haloform reaction
Similar to: I How it works: Chlorination of alkenes

Note how the anti product is
formed exclusively, through
backside attack on the
chloronium ion
Example 2: Conversion of alkenes to chlorohydrins

How it works: Chlorohydrin formation
In a nucleophilic solvent such as H2O, water will attack the

chloronium ion, forming a chlorohydrin
How it works: Electrophilic chlorination
a Lewis acid such as FeCl3 acti-

vates Cl2 towards attack by the
aromatic ring.
Example 6: Conversion ot enolates to

In the second step, electrophilic aromatic substitution
results in replacement of C–H by C-Cl
How it works: Chlorination of ketones under acidic conditions

Example 7: Radical chlorination of alkanes to alkyl chlorides

Index Index
22 23
2
Cyanide ion
How it works: Chlorination of enolates -

N
Same as:
Example 1: As a nucleophile in substitution reactions

Deprotonation of the ketone by strong base
results in an enolate, which then attacks Cl2
Example 2: Formation of cyanohydrins from aldehydes/ketones
How it works: Chlorination of alkanes
How it works: Nucleophilic substitution
Cyanide ion is a good

nucleophile but a
weak base (pKa of 9)
How it works: Hoffmann Rearrangement
How it works: Benzoin condensation
Carbonyl
addition
Here, the proton is transferred
betweeen carbon and oxygen
Expulsion
of cyanide

Index Index
24 25
CrO3 CrO3
Chromium trioxide
3
- How it works: Oxidation of primary alcohols to carboxylic acids
Similar to:
When aqueous acid is present 4 7
7 4 4
Hydrate
Water is a strong enough base to
deprotonate here
After proton transfer Second deprotonation results in

formation of the carbonyl
Example 3: Oxidation of primary alcohols to carboxylic acids
How it works: Oxidation of primary alcohols to aldehydes
proton transfer
pyridine (a base)

Index Index
26 27
CuBr

-
Similar to: Similar to:
How it works: Formation of aryl bromides How it works: Formation of aryl chlorides from aryl diazonium salts
Donation of an electron by Donation of an electron by

Cu(I) to give Cu(II) Cu(I) to give Cu(II)
Driving force for this reac- Driving force for this reac-
tion is loss of nitrogen gas! tion is loss of nitrogen gas!
The radical then abstracts Br The radical then abstracts Cl

from CuBr2,, giving CuBr from CuCl2,, giving CuCl

Index Index
28 29
CuI DCC
N,N
Also known as:
Similar to:
Example 1: Formation of amides from carboxylic acids and amines
How it works: Formation of organocuprates
How it works: Formation of amides from carboxylic acids and amines
Proton transfer
Now the amine
BEE attacks!
Amide
This byproduct is called a “urea”

(formed after proton transfer)

Index Index
30 31
DMS CH2 2
Also known as:
Similar to: Example 1: Conversion of carboxylic acids to methyl esters
Example 2: Cyclopropanation of alkenes
How it works: Reductive workup for ozonolysis

3
Example 3: In the Wolff Rearrangement
How it works: Formation of methyl esters
How it works: Wolff Rearrangement
Addition
Eliimination
DMSO
Heating leads to
loss of N2 gas
Tautomerism
(after proton transfer)

Index Index
32 33
D DIBAL
Deuterium
hydride
Also known as:
-
4
-
Similar to: 4 3
Example 1: Deuterium reagents as acids Example 1: Reduction of esters to aldehydes
Low temperature is
important to prevent further
reduction
Example 2: Reduction of ketones to secondary alcohols
Example 2: Hydroboration of alkenes
Example 3: Reduction of aldehydes to primary alcohols
Example 3: Reduction of ketones

Example 4: Reduction of nitriles to aldehydes
The reaction initially forms
an imine, which is then
hydrolyzed by acid
Example 5: Reduction of acyl halides to aldehydes
Low temperature is
important to prevent further
How it works: Deuterium as a reagent
reduction

Index Index
34 35
DIBAL DMP
Dess-Martin Periodinane
How it works: Reduction of esters to aldehydes
Similar to: 3
Next, hydride is At low tempera-

is coordination delivered to the tures the product
of the oxygen carbonyl carbon is stable until
lone pair to the acid or water How it works: Oxidation of alcohols
aluminum is added to
quench.
How it works: Conversion of nitriles to aldehydes
Deprotonation by acetate
ion gives acetic acid.
Imine
formation
Coordination of the Delivery of hydride to coordinates to DMP
nitrogen lone pair to the nitrile carbon Deprotonation
and displaces acetate
the aluminum
Dissociation of acetate
Aldehyde ion and deprotonation of
the C-H bond leads to
oxidation of the alcohol.
Hydrolysis gives
an aldehyde

Index Index
36 37
Fe FeBr3
Iron
Also known as:

-
Similar to: 3 3 3
Similar to:
Example 1: Reduction: conversion of nitro groups to primary amines
How it works: Reduction of nitro groups
How it works: Electrophilic bromination
This is a more electrophilic source of bromine

than Br2
3 3

Index Index
38 39
FeBr3 3
How it works: Friedel-Crafts Acylation Also known as:
Similar to: 3 3 3
Acylium ion
How it works:
3 3 3
Br
EF g

Index Index
40 41
Grignard Reagents Grignard reagents
Also known as: Example 6: Reaction with epoxides
Similar to:
Example 7: Reaction with carbon dioxide
Example 1: Conversion of alkyl or alkenyl halides to Grignard reagents
Example 8: Reaction with acidic hydrogens
Example 2: Conversion of aldehydes to secondary alcohols
Example 3: Conversion of ketones to tertiary alcohols How it works: Addition to aldehydes and ketones
Example 4: Conversion of esters to tertiary alcohols
Example 5: Conversion of acyl halides to tertiary alcohols

Index Index
42 43
Grignard Reagents H2
Hydrogen
How it works: Addition to epoxides
How it works: Addition to esters
Addition of Grignard Elimination of the OR group

reagent to the ester then forms the ketone
A second equiv-
alent of Grignard
reagent then adds
to the ketone
Finally, acid [HX here]

is added to obtain the
neutral alcohol

Index Index
44 Acid Acid 45
H +
H3O +
Anhydrous Acid Aqueous acid
4 3 4
4 3 4
Aqueous acid protonates
the negatively charged alkoxide,
Example 1: Acidic workup giving the neutral alcohol
Example 1: Acid workup
many similar examples of aqueous

workup throughout the Reagent Guide
Example 2: Hydration of alkenes to give alcohols
3
An equivalent reagent here
would be H2SO4/H2O
Example 2: To make neutral species into better leaving groups
Example 3: Opening of epoxides to give trans diols
4
3 4 Reaction proceeds through protonation

of oxygen followed by attack of water at
most substituted position
Example 4: Hydrolysis of esters to give carboxylic acids
nucleophiles)
Amides, nitriles, imines, and enamines can also be hydolyzed

by aqueous acid.
Example 5: Hydrolysis of acetals to give ketones
Protonation of a carbonyl
oxygen by H+ is a key step in
many reactions
– very reactive carbon!

c
Index Index
46 47
HBr HBr
How it works: Addition to alkynes
Attack of bromide
Similar to: upon carbocation
Note that the bromine adds to the Formation of most

most substituted carbon: stable carbocation
“Markovnikov” selectivity
Attack of bromide
upon carbocation
Formation of most
stable carbocation
How it works: Formation of alkyl bromides from alcohols
-
N
backside
protonation attack
Note here that the bromine

adds to the least substituted
carbon: attack of bromide ion
“anti-Markovnikov” selectivity
protonation
N
2)
Primary alcohol,
hence SN2 here. How it works: Free radical addition of HBr to alkenes
N
1)
heat or light
Tertiary alcohol,
hence SN1
only a catalytic amount of perox-

How it works: Addition to alkenes Propagation step 1: ides are required to initiate the
Step 1: protonation of alkene to Step 2: attack of bromide ion on reaction
give most stable carbocation the carbocation Here, bromine radical adds to the alkene.
Propagation step 2: Note that addition occurs at the less sub-
stituted carbon; this gives rise to the most
stable free radical (secondary in this case)

Index Index
48 49
Similar to:
Attack of chloride
upon carbocation
Note that the chlorine adds to the
most substituted carbon:
“Markovnikov” selectivity
Formation of most
stable carbocation
Attack of chloride
upon carbocation
Formation of most
stable carbocation
How it works: Formation of alkyl chlorides from alcohols
N
2)
N
Primary alcohol,
therefore SN2 backside attack
most likely of Cl
protonation
N
1)
Reaction proceeds via backside
Tertiary alcohol, attack on the primary carbon
therefore SN1 here
How it works: Addition to alkenes N
Step 1: protonation of
alkene to give the most
Step 2: attack of chloride ion on
stable carbocation attack of bromide ion
the carbocation
protonation
loss of
leaving
group

Index Index
50 51
H2CrO4 H2CrO4
Chromic acid
How it works: Oxidation of aldehydes to carboxylic acids
Also known as:
K 7 3 7 3 4 3 4 3 3 3
aldehyde
hydrate
Similar to: 4
Example 1: Oxidation of secondary alcohols to give ketones
Example 2: Oxidation of primary alcohols to give carboxylic acids
The base here can be

water or the conjugate
base of the acid
How it works: Oxidation of alcohols
Chromic acid
Water is basic
enough to
remove a proton
here

Index Index
52 53
2 2
Mercuric Acetate
How it works: Oxymercuration of alkynes

- Treatment of an alkyne with Hg(OAc)2 and water leads to the formation of an
enol, which converts to a ketone through tautomerization.
4 4
Similar to:
Attack of water at
the most substituted
carbon (Markovnikov
addition)
Acid replaces the
Tautomerization mercury with H
Tautomerization favors the

ketone
How it works: Oxymercuration of alkenes
attack at most substituted carbon

(“Markovnikov” addition)
mercurinium ion
NaBH4 converts the C–Hg

bond to a C–H bond
The reduction goes through a free radical on carbon,

so there is no syn/anti selectivity

Index Index
54 55
HgSO4 HI
Hydroiodic acid
3 4
Similar to:
Similar to:
Note that iodine adds to the most

substituted carbon (Markovnikov
selectivity)
How it works: Oxymercuration of alkynes
geminal diiodides
Formation of mercurinium
ion
N
2)
Deprotonation Primary alcohol

goes through
an SN2 process
Attack of H2O
N
1)
Note - Markovnikov selective
Tertiary alcohol can form a
relatively stable carbocation,
therefore an SN1 process is
Enol favorable
Example 6: Conversion of ethers to alcohols and alkyl iodides
How it works: Addition to alkenes

Loss of mercury
Attack of enol on
Tautomerization H2SO4
Step 1: protonation of
alkene to give the most Step 2: attack of iodide ion on the
stable carbocation carbocation

Index Index
56 57
HI HIO4
Periodic acid
Attack of iodide Similar to: 4 4
Alkenyl iodide
Example 1: Cleavage of diols to give aldehydes/ketones
(vinyl iodide)
Formation of most
stable carbocation
Formation of most
Attack of iodide stable carbocation
How it works: Conversion of alcohols to alkyl iodides

N How it works: Cleavage of diols to give aldehydes/ketones
Nucleophilic attack
Protonation
Carbocation formation
How it works: Cleavage of ethers
N N
Protonation Backside attack

Nucleophilic attack
Protonation
Notice how iodine starts in the

Carbocation formation (VII) oxidation state and goes to
(tertiary) (V) (it has been reduced)
2
Index Index
58 59
3
Also known as: 4 3
4
H2SO4 is a catalyst in this
reaction
carboxylic acids
Diazonium salt This reaction is often introduced

Note: other acids beside HCl can be used in the context of carbohydrate
as the acid here (such as H2SO4) chemistry. Note how the top and
botttom carbons have both been
How it works: Formation of diazonium salts oxidized.
-
4
How it works: Nitration of aromatics

Acid activates the N=O bond 4 3
toward attack by the amine
Loss of water
proton Protonation
transfer Nitronium ion
Step 1:
Electrophilic addition
proton
transfer Step 2: Deprotonation
4
+ H2O Note that acid is regenerated
Diazonium salt here; it acts as a catalyst in
this reaction.
f
Index Index
60 61
H2O2 H2O2
Hydrogen peroxide
How it works: Oxidative workup for ozonolysis
Example 1: As an oxidant in the hydroboration reaction
Note that carbox-

ylic acids (not
aldehydes) are the Ozonide Addition of H2O2
products here (breaks open upon to aldehyde
heating)
How it works: Hydroboration of alkenes
Proton transfer
Deprotonation
step is the rate-limiting step; it

Attack of peroxide Rearrangement is greatly accelerated by addi-
tion of base.
Carboxylic acid
Hydrolysis

Index Index
62 63
H3PO4 H2SO4
Phosphoric acid
3 4
4
Similar to: 4
Similar to: p
Example 1: Elimination of alcohols to give alkenes
Example 1: Elimination – conversion of alcohols to alkenes
How it works: Elimination of alcohols to give alkenes How it works: Elimination of alcohols
4
-
4
Protonation Loss of H2O
Carbocation
Deprotonation to Protonation formation
give alkene
Deprotonation
Note resonance stability of

the HSO4– anion
H2SO4 is regenerated
(i.e. it is a catalyst)

Index Index
64 65
I2 Iodine
Iodine
How it works: Iodination of ketones
Similar to: N
tautomerization
How it works: The haloform reaction

Example 2: Conversion of alkenes to iodohydrins
3
H+ here refers to any

generic strong acid
Enolate formation Iodination
Enolate
acids formation
Iodination
How it works: Iodination of alkenes

-
Attack of The enantiomer Enolate Iodination

alkene upon Nucleophilic will also be formation
iodine attack formed in this
example.
Iodonium ion Na+
3
A halohydrin
Elimination of the –CI3 Extra detail: under the
Addition of –OH ion (a weak base) basic reaction condi-
tions, the carboxylic acid
will be deprotonated.
Acidic workup required.
2
66
KMnO4
Potassium permanganate
Index
To
Index
KMnO4
67
How it works: Oxidation of primary and secondary alcohols
Similar to: K 7 4 3
Note: this is a potentially reasonable mechanism,

but the actual mechanism is complex and can Proton transfer
go down different pathways (some involving free
radicals, and some not fully understood!) Take
this with a grain of salt.
ylic acids
Aldehyde hydrate
Again, a suggested mechanism here, but KMnO4

oxidation can occur via multiple pathways (beyond
the scope of our discussion).
Note that the stereochemistry

of the diol is “syn” How it works: Oxidation of aromatic side chains
Note: only carbons adjacent

Note that this carbon
to the ring with at least one
lacks a C–H bond; it
C–H bond will be oxidized.
is not oxidized

Index Index
68 69
KMnO4 KOt-Bu
Potassium t
How it works: Dihydroxylation of alkenes Also known as: 3 3
4
t
4
Similar to:
or “Hofmann” alkene products)
In the absence of base, diols undergo Base (KOH) cleaves the

oxidative cleavage (see below) cyclic Mn compound
(“manganate ester”).
Hofmann product Zaitsev product
(major) (minor)
proton
transfer 3 3
How it works: Formation of “non-Zaitsev” elimination products
Acid workup leads to

the diol
How it works: Oxidative cleavage of alkenes

Steric clash
KMnO4 is protonated to give HMnO4 and adds to the alkene as above: “non-Zaitsev” or “Zaitsev”pathway
“Hofmann” pathway
Disfavored
Favored
Oxidative
cleavage
Addition
“cyclic manganate
Oxidation to carboxylic
ester”
acid (as above)

Index Index
70 71
KPhth LDA
Also known as:
Similar to:
-
Example 1: Conversion of ketones to enolates
Note that deprotonation Diisopropyl amine

occurs at the least sub-
stituted carbon
with NH2NH2) Example 2: Eiimination of alkyl halides to give “Hofmann” alkenes
“Hofmann” alkene product “Zaitsev” product

(major) (minor)
How it works: Substitution reaction How it works: Formation of less substituted enolates (“kinetic” enolates)
Tetrahydrofuran (THF) is a
common solvent for this reaction.
Low temperature maximizes
selectivity.
(Resonance forms of the Diisopropylamine (the con-

enolate) jugate acid of LDA)

Index Index
a
72 73
Li Li
Lithium
How it works: Birch reduction
-
3
t-
-
Similar to:
Example 1: Conversion of alkyl halides to alkyllithiums
when an electron donating group

such as OMe is present, protonation
occurs on the meta position
Example 2: Conversion of alcohols to alkoxides
Although t-BuOH is the most common

How it works: Formation of organolithium reagents alcohol used, MeOH, EtOH or i-PrOH
are all effective.
This is called a “radical

anion” Note that protonation
occurs adjacent to
the electron with-
drawing group
Alkyllithiums: strong bases and

excellent nucleophiles.

Index Index
74 75
4
Also known as: 3

Also known as:
cis 3
trans
Similar to: 3 Similar to: 4 3
How it works: Partial hydrogenation
cis
Quinoline

Index Index
76 77
4
t- 3
How it works: Reduction of esters, amides, and nitriles Also known as: 3 3
4
4
Reduction of esters: Similar to: 4 4
Example 1: Reduction of acyl halides to aldehydes
Acyl bromides will

react similarly
The reaction does not stop at the
aldehyde stage, going straight
through to the alcohol
How it works: Reduction of acyl chlorides
Reduction of amides:
Iminium
Here, oxygen is a better leaving ion
group than nitrogen!
Reduction of nitriles:

Index Index
78 79
m-CPBA m-CPBA
m-
acid
How it works: Baeyer-Villiger reaction
Similar to: 3 3 3 3
Addition
Proton
transfer
Migration
(key step!)
How it works: Epoxidation of alkenes

Proton
Minor note: the rate of the addition reaction
transfer
is increased by adding base, which depro-
tonates the peroxyacid, making it a better
nucleophile.
m-chloro benzoic acid

(byproduct)

Index Index
e
80 81
Mg
Magnesium
Similar to:
Similar to:
Example 1: Conversion of alcohols to alkyl mesylates
Example 1: Conversion of alkyl halides to Grignard reagents
It is common to use a
Diethyl ether is a common weak base (pyridine in
solvent for this reaction this example) to react
with the HCl that is
Example 2: Conversion of alkenyl halides to Grignard reagents formed as a byproduct
of this reaction. This
helps the reaction pro-
ceed to completion.
How it works: Formation of Grignard reagents

-
Here, magnesium donates a single electron to Br, which forms a radical an-
ion. Homolytic fragmentation of the C–Br bond leads to a free radical, which
recombines with MgBr to give the Grignard reagent.

Index Index
82 83
3
Sodium
Similar to: 3 3
Similar to:
trans alkenes
Dimethyl sulfoxide
(DMSO) is a common
solvent for SN2 reactions
Example 2: Conversion of alcohols to alkoxides
How it works: Nucleophilic substitution

- How it works: Reduction of alkynes to trans-alkenes
3
not covered in Org 1/

Org 2, but these types
How it works: Curtius rearrangement of radicals can easily
The preference interconvert between
for trans geometry geometries
can be explained
by the fact that
Addition Elimination these anions repel
each other such Protonation (by The solvent in these
Acyl azide that they maximize solvent) types of reactions is
their distance ammonia (NH3)
apart
Trans alkene
Isocyanate Amine
Index Index
84 85
4
How it works: The Birch Reduction -
Similar to: 4
3 3
When an electron donating group

such as OMe is present, protonation
occurs on the meta position
Example 2: Reduction of aldehydes to primary alcohols
The alcohol need not be t-BuOH; ethanol

(EtOH), methanol (MeOH) and isopropa-
nol (iPrOH) are all effective.
How it works: Reductions of aldehydes and ketones
Note that protonation

occurs adjacent to
Addition
the electron with-
drawing group
Protonation This reaction is

commonly performed
in a solvent such
as CH3OH, which
serves as a source of
protons.

Index Index
86 87
4 3
Sodium triacetoxy
How it works: In the oxymercuration reaction

4
Similar to: 3 4
rarely covered in textbooks
The C–Hg bond is weakened

Hydride attacks Hg, displacing and breaks homolytically to
the acetate ion give a carbon radical
How it works: Reductive amination

The carbon radical then
abstracts hydrogen from 3
the resulting Hg(I), giving 3
Net result is replacement of elemental mercury as a

mercury for hydrogen. product.
4 4

Index Index
88 89
3
Sodium Hydride
Similar to: 4 3
Similar to:
Example 3: Deprotonation of phosphonium salts to form ylides
How it works: Reductive amination

How it works: Deprotonation
imine
iminium
imine
amine
3 4

Index Index
90 91
4 2
Sodium periodate Sodium amide
Also known as:
-
Similar to: 4 4
Similar to:
How it works: Oxidative cleavage of diols to give aldehydes/ketones

“Geminal” dihalide -
has two halogens on
the same carbon
Attack of oxygen “Vicinal” dihalide -

on iodine (followed has two halogens on
Attack of second oxygen
by proton transfer) adjacent carbons
on iodine (followed by
another proton transfer)
Key oxidative
cleavage step! This proceeds
through an aryne
mechanism
How it works: As a strong base
Trivial detail: this usually loses

water to give NaIO3 plus H2O

Index Index
92 Base 93
Sodium hydroxide
Sodium Ethoxide
Also known as: 3
Similar to:
Equivalent to 3
E2 mechanism.
Hydrogen and leaving
group (Br) must be
“anti” . Heat helps to
promote elimination.
N
2) of alkyl halides
works best for primary
alkyl halides. With sec-
ondary, E2 competes
Example 3: Reaction with acyl halides to form esters

Also works for anhydrides
carboxylic acids How it works: E2 Reaction

Note “anti” relationship of
H and Br
triple line means

“same as”
Same reaction,
drawn as chair

Index Index
94 95
N–Bromosuccinimide
How it works: Allylic bromination
Similar to: N N Generation of Br2
This byproduct is
called “succinimide”
Initiation step
Example 2: Conversion of alkenes to bromohydrins
Propagation step 1
Bromohydrin
How it works: Halohydrin formation
Propagation step 2
Trans product
Bromonium ion formation
Top view
Side view
+ succinimide
Attack by solvent
(water in this case) Deprotonation
(Enantiomer)
2
Index Index
96 97
N– N–Iodo Succinimide
Similar to: I
Similar to: N N
Example 1: Conversion of alkenes to chlorohydrins Example 1: Conversion of alkenes to iodohydrins
How it works: Iodohydrin formation

How it works: Formation of chlorohydrins
Iodonium ion
Chloronium ion
Note - the
enantiomer is
also formed
here

Index Index
98 99
2
OH 3
Ammonia
Also known as: 3
Example 1: Conversion of ketones/aldehydes to oximes
Oxime
How it works: Conversion of ketones/aldeydes to oximes

How it works:
3
Proton
Addition transfer
Elimination
Oxime
Deprotonation
How it works: Beckmann rearrangement
Protonation Rearrangement
Oxime
Deprotonation
Nitrile

Index Index
100 101
2 2
B
2
cis
Similar to:
How it works: Partial reduction of alkynes.
4
-
syn
How it works: The Wolff-Kishner reaction

-
hydrazone
Deprotonation
Resonance Protonation
Although this species is often

drawn in the mechanism, it Protonation
likely does not exist as
the free carbanion. Deprotonation
Alkane
or
Index Index
102 103
O3 O3
How it works: Reductive workup
Similar to: 4
to aldehydes/ketones
DMSO
How it works: Oxidative workup
to carboxylic acids/ketones
Ozonide (decomposes Addition

upon warming)
How it works: Oxidative cleavage of alkenes

Proton
transfer
Deprotonation Trivial detail - the deprotonation step

is rate-limiting, so the reaction can
“Molozonide” be accelerated by the addition of a
base such as NaOH
Reduction

Index Index
104 105
R2CuLi RLi
Organocuprates
Also known as:
-
-
N
Similar to:
Similar to: Example 1: Conversion of alkyl halides to organolithiums
Example 1: Conversion of alkyllithiums to organocuprates
Example 2: Conversion of aldehydes to secondary alcohols

Acid is added in the
second step to protonate
, unsaturated ketones
the negatively charged
This reaction works best oxygen
for methyl, allyl, and benzyl
halides Example 3: Conversion of ketones to tertiary alcohols
Acid is added in the
second step to protonate
N
2) the negatively charged
oxygen
Example 4: Conversion of esters to tertiary alcohols

Organolithium reagents
add twice to esters,
acid halides, and anhy-
drides
Example 5: Conversion of acyl halides to tertiary alcohols

add twice to esters,
acid halides, and anhy-
drides
How it works: As a nucleophile
add to the less substituted
end of epoxides. Acid is
Electronegativity Due to carbon’s higher electronegativity
added to protonate the
relative to Cu, it bears a partial positive
negatively charged oxygen.
charge and is thus nucleophilic.

Index Index
106 107
R–Li R–Li
Example 7: Reaction with carbon dioxide How it works: Addition to esters / acid halides / anhydrides
Example 8: Formation of organocuprates
Addition
Example 9: As a base
Elimination of alkoxide
Organolithium reagents provides a ketone
are extremely strong
bases.
A second addition of
organolithium reagent
then occurs on to the
new ketone
Example 10: Addition to carboxylic acids Organolithium reagents
can add to carboxylic
acids if 2 equivalents
Addition of acid gives
are added. HX the neutral tertiary
How it works: Addition to aldehydes/ketones alcohol
behaves much like
How it works: Addition to epoxides
Addition Protonation
Addition Protonation

Index Index
108 109
OsO4 4
Osmium tetroxide Lead tetraacetate
Also known as:

-
syn 4 4
Similar to: 4 Similar to: 4 4
The stereochemistry of
this reaction is always
“syn”
In the lab, KHSO3 helps to remove the

osmium from this reaction. Its pres- How it works: Cleavage of diols to aldehydes/ketones
(as shown here)
How it works: Dihydroxylation of alkenes
(formed after proton

transfer)
Coordination
3 3
Coordination (and subsequent

proton transfer)
Oxidative
cleavage

Index Index
110 111
PBr3 3
Similar to: Similar to: 3
bromides chlorides
How it works: Formation of alkyl bromides from alcohols How it works: Formation of alkyl chlorides from alcohols
How it works: Formation of acyl bromides How it works: Formation of acyl chlorides from carboxylic acids
Attack of oxygen Addition Attack of oxygen

on phosphorus on phosphorus Addition
Elimination Elimination
Deprotonation Deprotonation

Index Index
112 113
5
P2O5
Phosphus pentoxide
- Also known as: 4
Similar to: 3
Example 1: Formation of alkyl bromides from alcohols Similar to: 4
Example 1: Conversion of carboxylic acids to anhydrides
Example 2: Conversion of amides to nitriles

Example 2: Formation of acid bromides from carboxylic acids
How it works: Conversion of carboxylic acids to anhydrides
How it works: Formation of alkyl chlorides and acyl chlorides

Carboxylic
Proton transfer acid #2
3 3
Carboxylic acid #1
Deprotonation Elimination
Anhydride
How it works: Conversion of amides to nitriles
Proton transfer
Addition
Elimination
Amide
Deprotonation
Nitrile
Index Index
114 115
Pd/C Pt
- Also known as:
syn
How it works: Hydrogenation
syn
How it works: Hydrogenation
syn
e
Index Index
116 117
PCC 3
Similar to: 3
Similar to: 4 3
How it works: Oxidation of primary alcohols to aldehydes Example 2: Conversion of amides to nitriles
How it works: Elimination of alcohols to alkenes
Addition
Proton transfer
Loss of chloride
Elimination Attack of oxygen on
of Cl phosphorus
Use of pyridine as a base

Elimination: Elimination
here will speed up the
formation of C–O
reaction considerably.
bond
Pyridinium chloride
(byproduct)

Index Index
118 119
PPh3 Pyridine

-
3
Similar to: Similar to: 3
Example 1: Conversion of alcohols to tosylates or mesylates

Pyridine acts as a
weak base in this
reaction, neutralizing
the HCl generated
here.
How it works: The Wittig reaction How it works: Formation of tosylates/mesylates
Deprotonation
SN2 with strong base
Phosphonium salt Note that the role of pyridine

here is simply to act as a base,
removing the HCl generated
during this reaction.
“oxaphosphatane” “Pyridinium chloride”

Ylide
Driving force for this
Breakdown of the oxaphosphatane gives
reaction is formation of
an alkene and triphenylphosphine oxide
the strong P=O bond
this is “triphenylphosphine oxide”

Index Index
120 121
RO–OR
Peroxides
Note that Br adds to the

less substituted carbon
“anti-Markovnikov”
How it works: Free radical bromination
This example shows the formation

of the thioacetal from the ketone
using 1,3-propanedithiol and BF3
How it works: Reduction of thioacetals

Index Index
122 123
SO3 SOBr2
Similar to: 3
Example 1: Conversion of alcohols to alkyl bromides
How it works: Formation of sulfonic acids

3 3
3 3
Example 2: Conversion of carboxylic acids to acyl bromides
Often written
HSO4–
How it works: Formation of alkyl bromides

Identical in all respects to SOCl2 (see section)
3
Note that H2SO4 is regenerated

in this step; it is a catalyst here.
3 3
SO3 is lost as a gas
H2SO4
This allows for formation of the ortho chlorinated

product without any para substituted product
because the SO3H “blocked” the para position

Index Index
124 125
2
Sn
Tin
Similar to: 3
Similar to:
Example 1: Conversion of alcohols to alkyl chlorides
Example 2: Conversion of carboxylic acids to acyl chlorides Reduction of nitro groups
loss of water
How it works: Formation of alkyl chlorides

N
Sn donates electron pair
How it works: Formation of acyl chlorides
Addition of Sn donates electron

chloride Hydroxylamine
Attack at Elimination of pair to N=O (nitroso)
sulfur chloride
loss of water
Acyl chloride
Sn donates electron pair Amine
Deprotonation Elimination of
oxygen
I
Index Index
as
128 129
TsOH
p p
Similar to: 4
Example 1: Conversion of alcohols to alkyl tosylates
Similar to: 4
How it works: Acid-catalyzed elimination of alcohols to give alkenes
Example 2: Substitution of tosylates

Formation of
a carbocation
Example 3: Elimination of tosylates
Protonation makes OH a better Deprotonation to

leaving group form an alkene
How it works: Tosylates as leaving groups
Note how the negative charge on oxygen can be delocalized

on to the other oxygen atoms through resonance.
Note that TsOH is regenerated here

(it is a catalyst in this reaction)

Index Index
130 131
Zn Zn/Cu
Zinc
Similar to:
alkenes
aldehydes/ketones
How it works: Cyclopropanation of alkenes

-
How it works: Reduction of ozonides
Ozonide

Index Index
132 133
Odds And Ends
Ethylene glycol
Example 1: The Clemmensen Reduction
Note: these reactions tend to KHSO3

work best on ketones adjacent
to aromatic rings.
How it works: The Clemmensen Reduction

amalgams
Oxalyl chloride
See a reagent in your introductory course or textbook
Click To Leave Feedback

Index Index
134 135
Methyl Ac acetyl
Me
Et Ethyl
Ts
Pr Propyl
Bu Butyl p-toluenesulfonyl
(tosyl)
i isopropyl Ms methanesulfonyl
(mesyl)
s sec-butyl Bs
i isobutyl
p-bromobenzenesulfonyl
(brosyl)
t tert-butyl
Allyl
phenyl
6
H5–)
Propargyl
H5CH2–) benzyl
6 Piv Pivaolyl

Index Index
136 137

Index Index
138 139

Index Index
140 141

Index Index
142 143
Reducing Agents

Index Index
144 145
Reducing Agents

Index Index
146 147

Index Index
148 149
r

Index Index
150 151
Types of Arrows

Index Index
152 Reagent 153
Protecting Groups
Protection of alcohols 3
Deprotection: TBAF or
aqueous acid
-
Silyl ether
Deprotection: aqueous Example 1: Ring closing metathesis

acid
Acetal
Example 2: Cross metathesis

Deprotection: aqueous
acid or base The squiggly line indicates a mixture of
Ester cis and trans isomers
Protection of aldehydes and ketones
acid
Acetal In practice, only works
well for strained alkenes
(like norbornene)
“norbornene”
acid
Acetal (cyclic)

Index Index
154 155
How it works:
-
Alkenyl halide:
also
work
Coupling partner: -
equals
Alkene Boronic acid Boronic ester Organostannane
Palladium sources:
3 4
3
-
Alkene
metathesis
product Coordination to
alkene
Catalyst
resting
state
Pd(PPh3)4 Pd2(dba)3 Pd(OAc)2
LIgands: -
Reverse 3
cycloaddition 3
#2
Cycloaddition Cycloaddition
#2
Triphenyl phosphine Tricyclohexyl Tri o-tolyl phosphine

(PPh3) phosphine (PCy3)
Coordination to
Reverse cycloaddition (forming
second alkene Additives:
ethylene byproduct)

Index Index
156 157
How it works: Heck reaction How it works: Suzuki reaction
Using NEt3 as a
base “mops up” the
HBr that forms
This step tends to

put Pd on the least
substituted carbon
(sterics)


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Example 1: Acetylation of alcohols

Example 2: Conversion of carboxylic acids to anhydrides

How it works: SN1 Reaction of alkyl halides

Many other catalysts

Activation of Ac2O Acylium ion

Attack of aromatic ring on Re-aromatization (often shown

Similar to: 3 Similar to:

How it works: Free-radical halogenation of alkenes

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Also known as: Also known as:

How it works: Friedel-Crafts acylation

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

How it works: Meerwein-Ponndorf-Verley Oxidation

Example 1: Conversion of ketones to thioacetals

How it works: Formation of thioacetals

The aluminum alkoxide can go on to

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

How it works: Hydroboration of alkenes How it works: Hydroboration of alkynes

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Similar to: acids

How it works: Bromination of alkenes

Example 3: Conversion of alkenes to halohydrins

How it works: Bromination of alkenes

Example 6: Conversion of ketones to

Example 7: Conversion of enolates to

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

How it works: Bromination of enolates

How it works: Halogenation of alkanes

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Example 8: The haloform reaction

Similar to: I How it works: Chlorination of alkenes

Example 2: Conversion of alkenes to chlorohydrins

In a nucleophilic solvent such as H2O, water will attack the

a Lewis acid such as FeCl3 acti-

Example 6: Conversion ot enolates to

How it works: Chlorination of ketones under acidic conditions

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

How it works: Chlorination of enolates -

Example 1: As a nucleophile in substitution reactions

How it works: Nucleophilic substitution

Cyanide ion is a good

How it works: Benzoin condensation

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

After proton transfer Second deprotonation results in

Example 3: Oxidation of primary alcohols to carboxylic acids

How it works: Oxidation of primary alcohols to aldehydes

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Also known as: Also known as:

Similar to: Similar to:

Donation of an electron by Donation of an electron by

The radical then abstracts Br The radical then abstracts Cl

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Also known as:

How it works: Formation of organocuprates

How it works: Formation of amides from carboxylic acids and amines

This byproduct is called a “urea”

Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Also known as:

Similar to: Example 1: Conversion of carboxylic acids to methyl esters