Facilitator: Chris Lovero Organic Chemistry Reactions 1

Task Reaction Notes

Addition of HX *Adds a halide

H H H Br to more substituted
(Mark) HBr
H CH3 carbon.
H CH3 H H

Addition of HX *Adds a halide

H H Br H
HBr
(Anti-Mark) to least substituted
H CH3
ROOR carbon.
H CH3 H H

Add two Br's anti *Anti and co planar

CH3 Br2 CH3
to alkene
CH2Cl2
Br
D
D (or CCl4) Br

Adding a Br and CH3 *Anti and co planar

CH3
OH (Mark w/ Br as H
Br2 OH
and anti-planar)
H2O D
D Br

Forming alkene *Wedges with wedges

H Br H H
from vicinal dihalide H NaI or KI and dashes with dashes
H3C CH3 *E2 Like!
Br acetone H3C CH3

Dehydration to *E1 like and it cannot

H2SO4
alkene give terminal alkene
OH
heat

*SPECIAL REACTION:
POCl3 dehydrates to form
OH
terminal alkene.
heat

Addition of OH CH3 CH3 *CANNOT CONTROL

(direct and mark) STEREOCHEM!

CH3 H3O+ CH3
*Low yield!
OH
*C+ formation!
Facilitator: Chris Lovero Organic Chemistry Reactions 2
Task Reaction Notes

Oxymercuration/ *Complex mechanism

CH3
demercuration
CH3 1) Hg(OAc)2/ H2O *Mark and antiplanar
OH
(Add OH from alkene 2) NaBH4
mark and antiplanar)
H
D D
*Complex mechanism
CH3
SPECIAL: Adds alcohol CH3 *Mark and antiplanar
instead to form ethers! 1) Hg(OAc)2/ CH3OH O CH3
*WILL BE SEEING THIS
2) NaBH4 H MORE IN ORGO II
D D

Hydroboration *Anti-mark

(Add Oh anti-mark and D D *Notice Peroxide

OH
syn planar) CH3
1) BH3 / THF CH3
2) H2O2 / -OH H

CH3 CH3
Catalytic Hydrogenation H 3C H3 C *Steric factors must be

(Alkenes -> Alkane, Syn payed attention to

D
H2
Addition of H) H3 C *Can use D2 instead
D
Pt, Pd, or Ni
H
CH3 H

*expensive
Formation of
CH3 OH *toxic
Vicinal Diols
OsO4 CH3 *great yield
(Syn)
H2O2
D D OH

CH3 OH *cheaper
*safer
KMnO4 CH3
*poor yield
D OH
cold, basic
D
Facilitator: Chris Lovero Organic Chemistry Reactions 3
Task Reaction Notes

Ozonolysis *Can use Zn/acetic acid

R R O O
1) O3 / CH2Cl2
(double bond cleavage) R + R instead of (CH3)2S
R R 2) (CH3)2S
R R *Can isolate the

R R formaldehyde.
1) O3 / CH2Cl2 O O
R + R
R H 2) (CH3)2S
R H

R H 1) O3 / CH2Cl2 O O
R + H
R H 2) (CH3)2S
R H

Warm KMnO4 *further oxidizes to form

R R O O
KMnO4 carboxylic acids
cleavage
R + R
warm *cannot isolate the
R R R R
formaldehyde
R R O O
KMnO4
R + R
R H warm
R OH

R H KMnO4 O

warm
R + CO2 + H2O
R H R

Carbene / Carbenoid *syn

CH3 CH3
addition (formation of CH2N2 *stereochem is preserved
cyclopropane) *Second reaction uses
heat
the Simmons-Smith
D
D reagent
H CH3
CH2I2 H CH3

H3C D Zn(Cu) D
H3C

Formation of epoxides *useful for synthesis

from alkenes CH3 (ESPECIALLY IN

CH3
MCPBA ORGO II)
O
D D
Facilitator: Chris Lovero Organic Chemistry Reactions 4
Task Reaction Notes

CH3 *acidic conditions opens

Opening of Epoxides CH3
from more substituted
H3O+ OH
side.
NOTE: Can use RO- O
H2O OH *Basic are like SN2
to form ethers. You D
D (least substituted side)
will see this in Orgo II.
CH3 OH *Please look up
-
1) OH CH3 mechanism.
O
2)H3O+
D
D OH
Formation of *please look up the
Cl Cl
H CH3 mechanism so you can
Dibromocarbenes and CHCl3 H CH3
Dichlorocarbenes see how the carbene
H3C D KOH
H 3C D is formed
CH3
CH3
CHBr3 Br
KOH
Br
D D
Formation of the *forms the nucleophile
NaNH2 -
acetylide anion H 3C C C H H3C C C that is handy when
connecting carbons!

with methyl or 1o halides *SN2 because of the

Uses of the acetylide
- CH3Br H3C C C CH3 exception we learned
anion H 3C C C
from before!!!!

with 2o or 3o halides Br *E2 remember from last

- H3C CH CH3 CH2
H 3C C C H3C CH test!!!

with carbonyl groups (ketones, aldehydes, and formaldehydes) *acetylide anion attacks
HO
partially positive carbon
O -
1) H3C C C H3C C CH3 *DO NOT FORGET
H3C C CH3
2) then H3O+ C then H3O+

C
H3C
Facilitator: Chris Lovero Organic Chemistry Reactions 5
Task Reaction Notes

Synthesis of Alkynes *Need either geminal or

Br Br 1) NaNH2 / 100oC vicinal dihalides
H3C CHCH CH3 HC C CH2 CH3
*Look up mechanism
2) H3O+
*NaNH2 gives terminal
Br Br
*KOH gives internal
CH2CHCH2CH3

Br
H3C C CH2 CH3
Br
Br
HC CH2 CH2CH3 KOH
H 3C C C CH3
Br 200oC

Br2 and alkyne H 3C H

Halogenation of alkynes *Stereochem cannot
be controlled
Br Br
Br2
H 3C C C H
(1 eq)
+
Br H

H 3C Br

HBr and alkyne *Mark

HBr Br H
*syn addition
(1 eq)
H 3C H
H 3C C C H
Br
HBr
(2 eq)
Br

HBr and alkyne *Anti mark

H Br *syn addition
HBr
H 3C C C H
ROOR
H 3C H

Catalytic reduction with *Takes it all the way back

reactive catalyst to alkane

H2
H 3C C C CH3
*generally bad yield
Pt, Pd, or Ni
Facilitator: Chris Lovero Organic Chemistry Reactions 6
Task Reaction Notes

Alkyne to Alkene: Lindlar's catalyst *isolates an alkene with

H H a SYN addition of H
TRIPLE to DOUBLE H2 / Pd(BaSO4)
H 3C C C CH3
quinoline
H 3C CH3

Dissolving metal *isolates an alkene with

H CH3
NaNH3 an ANTI addition of H
H 3C C C CH3
H 3C H

Addition of H-OH to Mercuric Ion *Mark addition

O
HgSO4 / H2O
alkynes C *If not terminal, you will
H3C CH2 C C H
H2SO4 H3C CH2 CH3 get a mixture.
*Formation of ketone
HgSO4 / H2O
O
H3C CH2 C C CH3
H2SO4 C
H3C CH2 CH2 CH3

+
O
C
H3C CH2 CH2 CH3

Hydroboration
*Antimark addition
O
1) Sia2BH *will get a mixture if not
H3C CH2 C C
C H
2) H2O2 / -OH H3C CH2 CH2 H terminal
*Formation of aldehyde

*Forms vicinal
Oxidation of alkynes KMnO4 / H2O O
H 3C C C CH3 carbonyls
(mild conditions) neutral / cold
*further oxidizes terminal
O alkynes to form
carboxylic acid.
KMnO4 / H2O O
H 3C C C H
neutral / cold OH
O
Facilitator: Chris Lovero Organic Chemistry Reactions 7
Task Reaction Notes

Cleavage of Alkynes: Oxidation of alkyne (strong) *Forms H2O and CO2

O
1) KMnO4 / H2O if terminal.
H 3C C C CDH2
H 3C OH
2) -OH / heat
+
O

HO CDH2
1) KMnO4 / H2O O
H 3C C C H + H 2O + CO2
-
2) OH / heat OH

Ozonolysis *Same products as

O O
1) O3 + previous
H 3C C C CDH2
2) H2O H3C OH HO CDH2

1) O3 O
H 3C C C H + H 2O + CO2
2) H2O
OH

The Grignard Reagent H Mg H *Forms from 1o, 2o, 3o,

H3C CH C H3C CH C
ether allyl, vinyl, and aryl
Br MgBr carbons.

The Organolithium Li *This reagent acts like

Reagent
H3C CH2 Br H3C CH2 Li grignard but is stronger.
pentane or hexane

Formation of alcohols 1o alcohols. (Grignard and formaldehyde) *Know this mechanism!

O
from Grignard *Carbon attachment
MgBr 1) H H
OH
2) H3O+

2o alcohols. (Grignard and aldehyde) *Know this mechanism!

O
*Carbon attachment
MgBr 1) H
OH
2) H3O+

3o alcohols. (Grignard and ketone) *Know this mechanism!

O
*Carbon attachment
MgBr 1)

2) H3O+ OH
Facilitator: Chris Lovero Organic Chemistry Reactions 8
Task Reaction Notes

Grignard and esters *Reaction goes until

O MgBr
OH
or acid halides completion

OCH3 1) *Know this mechanism!

+
2) H3O

Grignard and Epoxides *SN2 like (attacks least

(opening of epoxides) O 1)
MgBr
OH
substituted side)
2) H3O+ *Know this mechanism!

Attaching Deuterium to *This is just good to

H 3C MgBr D2O H 3C D
carbons know.

Corey-House Reaction *not well understood

Li CuI
CH3Br CH3Li (CH3)2CuLi (do not need to know
mechanism)
+
Br *another way to attach
carbons.

Hydride reduction of mild conditions (NaBH4 as reagent) *reduces only

carbonyls aldehydes and

O NaBH4 OH
ketones.
EtOH
*use alcohols as a

O NaBH4 solvent.
no reaction
EtOH
Cl

strong conditions (LiAlH4 as reagent) *reduces aldehydes,

ketones, esters, acid

O 1) LiAlH4 / ether halides, carboxyllic

2) H3O+ OH acids.
OH
*Use ethers solvents
*Two step process
O OH
1) LiAlH4 / ether +
O 2) H3O+ OH
Facilitator: Chris Lovero Organic Chemistry Reactions 9
Task Reaction Notes

Raney Nickel *Reduces both carbonyl

O H2 OH
and alkene.
Ra-Ni

Oxidation of alcohols 2o alcohols *any [ox] can be used

Na2CrO7
*KMnO4 and NO3 can
H2SO4 / H2O
be used but they are
harsh.
OH CrO3 / H2SO4 / H2O
O
acetone / 0oC

(Jones reagent)

PCC

CH2Cl2

1o alcohols
*PCC is the only one
Na2CrO7
that can isolate
H2SO4 / H2O OH
the formaldehyde.
O
CrO3 / H2SO4 / H2O
OH
acetone / 0oC

(Jones reagent)

PCC
O
CH2Cl2

Formation of the *RETENTION from

Tosylate Ester where alcohol was
TSCl
OH OTos
originally (SN2

purposes)

Formation of alkyl halide

from 3o alcohols HCl / ether

OH Cl
0oC
Facilitator: Chris Lovero Organic Chemistry Reactions 10
Task Reaction Notes
*Basically an SN2
Formation of 1o/2o
PBr3
Br CH3 reaction. (Inversion
alkyl halides from 1o/2o
CH2Cl2 from original alcohol)
alcohols
*Can also use SOCl2
PCl3
H3C OH Cl CH3 for Cl, but it undergoes
CH2Cl2
a special mechanism!

P / I2
I CH3
CH2Cl2

Unique cleavage with

O
OH *Vicinal diols must
HIO4 CH3 HIO4 CH3 be syn
OH H
H
O
Formation of Alkoxide 1o or 2 o alcohols
Nao
-
Anion OH O
2o or 3o alcohols Ko
-
OH O
-
Williamson ether O *Basically that SN2

synthesis H 3C Br exception we learned

O
in test 2

Ethers from intermolecular *Must be identical

dehydration H2SO4 alcohols or else you
2x CH3CH2-OH CH3CH2-O-CH2CH3
will get a mixture!!!
140oC

Pinacol - Pinacolone O *Need vicinal diols

OH OH
Rearrangement H2SO4 *Know mechanism
(methyl shift!)

Fischer Estherification H 3C CH2 OH + *CAN USE ACID

H
H3C CH2 O C CH3 HALIDE instead of
+
O carboxyllic acid!!!
HO C CH3
O