.

. .

)( ) (Structureal isomerisation
.
) (Fragmentation

.
:1 ) 20(
.
.
:2

.

:

. ) (
.

. .

.
.

.
... .

) (Hyperconjogation

p
.

)( .

) (1o ) (2o
) (3o . 16 67
.

 !
) (
.

C C
M

Migration

C C
M

M = Migrating group

CH3
CH2

H3C C
CH3

- H2O

CH3
H3C C CH2 OH2
CH3

Elimination

Me [1, 2] Shift

CH3
H3C C CH2
CH3

- H+

ClNucleophilic
substitution

HCl

H3C

CH3

H3C

CH3
H3C C CH2 OH
CH3

CH3
H3C C CH2
Cl CH3

.

.

H+

Me
Me
Me

H+

Me
Me
- H+

OH

Rearangment
Me

Me
Me
Me

- H2O

Me
Me
Me

OH

Me

) ( .

.
.

OH2

OH
H2SO4

- H+

KHSO4

Me
Me

Me

170 C

OH
Me
H
Me

Me

:

) (3 .


.
.

- H+

a
"Me" Shift

OH2

)(3
a
H

- H+

b
"Alkyl" Shift

)(3

b
)(2

- H2O

H+
Heat

OH

 :

)
(

OH

Ag+
H2O

AgNO3

. ) (
.

CH3
H3C C CH CH2
CH3

HCl

CH3
H3C C CH

CH3

"Me" Shift

CH3
(2)

CH3
H3C C CH CH3
(3) CH3

CH3 CH3

Elimination

CH3 CH3

- H+

Cl- Addition

CH3
H3C C CH CH3
Cl CH3





.

)

(

.










.

CH3

CH3

CH3

OH2

CH3

H+

CH3

H3C
CH3
H

CH3

CH2

CH3

OH

H3C

CH3

CH3

H3C

Rearangment

CH3
H3C

CH3
- H+
CH3

CH3

CH3

- H+
CH3

H+
H

CH3
H3C

CH3

CH3
H3C

CH3

H3C

CH3

H+
CH3

CH3

CH3

Rearangment
CH3

CH3

CH3
CH3

H3C

CH3

H3C

CH3

H3C

-H+
CH3
-H+
CH3

CH3

CH3

H+
CH3

CH3
CH3

H3C

CH3

H3C

CH3

H3C

 ) (
:

CH3

CH3
CH2

CH3

CH3

CH3

H+

CH3

OH

OH2

a) Elimination
- H+
b
H

CH3
CH3
a
bH
H

a
b) Rearangment

a
- H+

CH3
b

Not formed
Berdt - Low

H+
More active double bond

a
Not formed
exo cyclic
double bond
is unstable

- H+
b

H
b

H
O

H
O

-H

H
O
Metyl shift

OH

Rearangment

H3O+

Ring opening

.

.

.
.

HO

H3O+
O

H3O+

Alkyl shift

HO

HO

Rearangment

HO

HO

Rearangment

HO

HO

- H+

. .

 .

. .
.
) ( -
.

SnCl4 / Pentane
O

Cl4Sn O

Cl4Sn O

Cl4Sn O

H
- H+
O

HO

Cl4Sn O

Cl4Sn O

CH3
CH3

CH3

CH3
CH3
CH
CH3 3
O

CH3
H+

CH
CH3 3
CH3
O
CH
3
H

CH3
CH3

H
CH3
H3C

H
CH3

HO
H3C CH
3
Lanosterol

Cyclization

CH3

H
Rearangment

CH3

H3C

- H+

H
HO
H3C CH3

CH3

.
.

CH3 HgOAc

CH3

H2O
H3C

OH

HgOAc

Hg(OAc)2

CH3
H3C

H3C
H3O+

NaBH4
CH3

H3C OH
H3C

OH
Without rearangment

H3C
With rearangment

OH
H2SO4 50%

H2O
Rearangment
OH

1) Hg(OAc)2 , H2O
Whitout rearangment

2) NaBH4


) ( .
.
.
:
- )
(.

.
.
:

Br

Br

Br

Br
Rearrangment With
Ring Expanding

2, 6-Dibromocamphane

Br

Br2
- Br
-Pinene

 - .

.

. :

R1
C C CH2Cl
O R2

R3

- H+
Rearrangment

R1
R3 C C CH2Cl
H O R2

Cl2

R1
C C CH2
OH R2

R3

R1 = C6H5
R2 , R3 = H or alkyl

 -
.

) ( - Br .

.

:
Br

Br

Cl

Cl
Cl

Br

Cl
Cl
Cl

Cl
- Br2

Cl

Cl

Br

Cl

Cl
Cl

Cl
Cl

Cl
Cl

Cl

Cl

Cl

Br
- Br

Cl

Cl
Cl
Cl

Cl

.




.

:

Br Br3
Br2

Bromonium ion adamantyldeneadamantane

TiCl3

" "
.

.

.

:
Br
Br
O
O

O
O

a
Br

Br
Br
b

Br Br

Br a

O
O

O
O

 - 2 )(
- 2- . 350
.
K
OAc

Kexo / Kendo = 350

HOAc

+
OBs

OBS

Via

.


.
.

Cl

Cl

HCl