The material here is from Chap. 12 and is repeated in Chap. 12 slides.

TOSYLATES
 TOSYLATES

ALCOHOL + p-TOLUENESULFONYL CHLORIDE

O
R O + Cl S CH3 TsCl
H O
TOSYL CHLORIDE

pyridine

O
R O S CH3 ROTs
O

TOSYLATE ESTER
CONVERSION TO A TOSYLATE WITH TsCl AND PYRIDINE

Poor leaving TsCl

O
group ..
O R O S CH3
+
* .. Cl S CH3 H O
R O: -
O Cl
H ..
N

R-OTs
pyridine
O
R* O S CH3
O
H
+ Cl -
If the alcohol is Good leaving group N
chiral, the conversion for both SN1 and SN2
to a tosylate retains
configuration.
EXAMPLE OF THE USE OF A TOSYLATE

(R) (R)
TsCl
CH3-CH-OH CH3-CH-OTs
pyridine
Ph Ph
RETENTION
NaCN
S N2
acetone

INVERSION

(S)
CH3-CH-CN
Ph
EXPLANTION OF STEREOCHEMISTRY

Same configuration
Ph Ts Cl Ph as the starting alcohol.
..
H O: H O Ts
pyridine H3C
H3C
H
NaCN
The first reaction step acetone
does not involve the
carbon stereocenter - Ph
the atom oxygen reacts. This step is an
N C H SN2 reaction
CH3
with inversion
of configuration.
BROSYLATES
BROSYLATES WORK LIKE TOSYLATES
O
Cl S Br p -bromobenzenesulfonyl
R O + chloride
O
H
“Brosyl Chloride”
pyridine BsCl

O
a p -bromobenzensulfonate
R O S Br
O “Brosylate”
R-OBs
a good leaving group
ADENOSINE TRIPHOSPHATE

ATP
 NH2 R-O-H + ATP R-O-P or R-O-P-P or R-O-P-P-P

N N
O O O
N N
CH2 O P O P O P OH
OH HO
O O O O

triphosphate .. .. ..
:O-R :O-R :O-R
O O O
H H H
R O P O P O P OH

O O O O monophosphate
R O P OH
O O
O
R O P O P OH

O O diphosphate
PHOSPHATES (MONO, DI, AND TRI) ARE GOOD LEAVING
GROUPS FOR BOTH SN1 AND SN2 REACTIONS

O O
Nu:
R O P OH R O P OH

O O
S N2
SN1 (ionization)

.. .. .. ..
:O :O : :O : :O :
.. .. .. .. .. .. .. ..
:O P OH :O P OH :O P OH :O P+ OH
.. .. .. .. .. .. ..
:O: :O: :O :O
.. :
.. .. ..

resonance stabilized ion