Chemistry Reference
In-Depth Information
CF
3
Pd(nbd)Cl
2
(5 mol
%)
(
−
)-sparteine (20 mol
%)
PhCH
3
, MS3A, O
2
, 80
°
C
O
H
OH
O
NHBoc
NHBoc
NHCH
3
·HCl
Prozac
¨
57.5% conv., 93.1% ee
k
rel
17.9
Pd(nbd)Cl
2
(5 mol
%)
(
−
)-sparteine (20 mol
%)
Cs
2
CO
3
(0.5 equiv.)
t
BuOH (1.5 equiv.)
PhCH
3
, MS3A, O
2
, 80
CO
2
-
Na
+
HO
HO
O
H
OH
HO
S
Br
Br
Cl
N
°
C
Singulair
¨
70.6% conv., 99.9% ee
k
rel
15.3
F
3
C
CF
3
Pd(nbd)Cl
2
(5 mol
%)
(
−
)-sparteine (12 mol
%)
Cs
2
CO
3
(0.4 equiv.)
CHCl
3
, MS3A, O
2
, 23
OH
O
H
F
F
Me
O
F
C
°
CO
2
Me
CO
2
Me
NMe
N
HN
50.8% conv., 94.7% ee
k
rel
82.7
H
O
Merck's h-NK1 receptor antagonist
Scheme 11.8.
Pd[
(−
)-sparteine]Cl
2
1
(20 mol
%)
(−
TIPSO
TIPSO
)-sparteine (20 mol
%)
2-methyl-2-butene (20 mol
%)
CHCl
3
,Cs
2
CO
3
, O
2
, 23
OMe
OMe
OMe
O
O
O
O
O
O
N
OMe
OMe
OMe
°
C
HO
HO
(+)-Amurensinine
(±)-
3
(
)-
3
: 47%, >99% ee
−
Scheme 11.9.
substances including Prozac ® , Singulair ® , and Merck ' s h - NK1 receptor antagonist
reported by Stoltz and coworkers (Scheme 11.8) [16]. The total synthesis of (+)-amu-
rensinine, a member of the isopavine family that exhibits important biological activities
toward Alzheimer's and Parkinson's diseases, was also accomplished by using the pal-
ladium catalysis (Scheme 11.9) [17]. The racemic benzylic alcohol (
±
) -
3
was effi ciently
resolved to (
−
) -
3
with
>
99% ee.
11.2.3. Ruthenium Catalyst
Ruthenium complexes have been known to be effective catalysts for the aerobic
oxidation of alcohols [18]. In 2000, Katsuki and coworkers reported the fi rst example
of oxidative kinetic resolution of secondary alcohols with ambient air as the oxidant,
in which chiral (nitrosyl)ruthenium(salen) complex
4
is employed as precatalyst [19].
