Chandra
Kanta
De,
Eric
G.
Klauber,
and
Daniel
Seidel*


J.
Am.Chem.Soc.
ASAP


11/13/2009


• used
for
kineCc
resoluCon
and

desymmetrizaCon
processes
• enanCoselecCve
acyl
transfer
pathways


• III
could
be
a
beJer
acylaCng
agent
than
II,


• 
proper
choice
of
X‐
and
reacCon
medium
:
decrease
solubility

of
II
over
III


new
concept
for
asymmetric
nucleophilic
catalysis
:
kineCc
resoluCon
of
primary
amines.


De,
C.K.;
Klauber,
E.G.;
Seidel,
D.
J.
Am.Chem.Soc.
2009,
131,
XXXX


Fu, G. C.; Arai, S.; Bellemin-Laponnaz, S. Angew. Chem. Int. Ed. 2001, 40, 234-236.

Fu, G. C.; Arp, F. O. J. Am. Chem. Soc 2006, 128, 14264-14265.

Mioskowski, C.; Srseniyadis, S.; Valleix, A.; Wagner, A. Angew. Chem. Int. Ed. 2004, 43, 3314-3317.

List, B.; Hoffmann, S.; Nicoletti, M. J. Am. Chem. Soc 2006, 128, 13074-13075.

0.01
M
concentraCon
providing
the
best
s‐factor
20
mol
%
of
DMAP

improved
s‐factor
to
10


Lowering
of
both
catalysts:
s‐factors
slightly
reduced


De,
C.K.;
Klauber,
E.G.;
Seidel,
D.
J.
Am.Chem.Soc.
2009,
131,
XXXX


Only
DMAP:No
effect
on

reacCon
rate
no
DMAP
:
significant


amounts
of
enanCoenriched

product


Other
HB
catalysts:inferior

results


De,
C.K.;
Klauber,
E.G.;
Seidel,
D.
J.
Am.Chem.Soc.
2009,
131,
XXXX


in
the
absence
of
DMAP
:
HB
acCvaCon
of
the
anhydride



In
the
presence
of
DMAP:
B

dominates


De,
C.K.;
Klauber,
E.G.;
Seidel,
D.
J.
Am.Chem.Soc.
2009,
131,
XXXX


e
poor
:beJer

s‐factor