Review

X
EWG Not for
-CR3

OH
- KMnO4 or H2 (1 atm)
K2Cr2O7 Rh

OH COOH
EWG

1
 Suzuki-
Miyaura
Ph-B(OH)2
Review
rafts
Pd-(PPh3)4 F-TEDA(BF 4) 2 Friedel-C
CO32- o r Br , Cl 2 Acyl-Cl
FeX 3 f
2
Biaryl +AlCl 3
compounds Fr
ied
I el-
Cu2 for 2 Al
+
ky Cr Acylation
N
O 3
Aromatic l - C l +
af
ts
Halogenation
H SO 4
ring Al
Cl
H2 3

O2 1. No Cl-Ph 3. 3°: No
H2SO4 Enzymes C=C-Cl
+ stop
O SO3 FADH2
e/H H
3
Alkylation
F -O Nitration
2. Side products
with 1° alkyl
chloride
Sulfonation Hydroxylation

2
Electron donation/withdrawal property
of substituents affect ring reactivity and
orientation in electrophilic substitutions

Deactivator Activator
m-Directing o-/p- Directing
3
 Toluenesulfonyl
chloride
OH Review
-C–C- Smaller R SAM e- donation PPi
Lewis base Stable X-
SN1 HX for 3° Nu Polar with :O
ToS SN2 HF, SOClStable X -
X
PBr3 for 1° and 2°Polar aprotic-C–C-
2

-C–C- SN 2 HX °
SN2 SN1
-C–C-
for 1° &
2°
+ -
Nu X
RMgX
Mg * H
Li * * X2
Grignard
RLi -C–C- Anti-addition
*
R2CuLi CuI X X
Gilman E1cB E2 E1 C-C=C
X2
Alkane O HXStrong
basicity -C=C-
e- donation
Stable X - hν
=

-C-C-C- Markovnikov’s
of -Nu Polar with :O
–

F, NH2, OR OH Structure
4
 Predicting nucleophile actions
on alkyl halides
Substrate? → Strong base? → Solvent?
E1cB structure 1º polar
aprotic
O F SN2 solvent
=

-C-C-C- NH2 SN1/E1

–

OH OR E2 Strong
base

polar
aprotic
2º Neutral :O
3ºNeutral :O
Weak
solvent SN2 base solvent SN2 solvent
SN1/E1 SN1/E1
E2 Strong E2 Strong
base
base

5
X Y
Leaving group factor
Transition in SN2 reaction of
S 2
N
Which
leaves? state alkyl halides
Best leaving groups are those that best stabilize
the negative charge in the transition state
Conversion is needed
Low SN2 reactivity Chlorosulfite, phosphite
… convert to … Di- or monobromophosphite

~H2O
<<1 1 200 10 4
3 X 10 4
6 X 104