Fukuyama Group - Group Meeting Problems 2001/08/22

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Fukuyama Group - Group Meeting Problems
2001/08/22
H 2NOC
H 2N
O 2N
HO
HO
N
O
N
Bn
CONH 2
CH 2CH 2OCOPh
O
Cl
+
hν
H2O acetone
O *
*) as acid scavenger
OHC
1) NaNO 2
6 N HCl
–45 °C to rt
2) N
N
N
H
POCl3, Et3N CH3CN hν (pyrex)
MeOH
carboxylic acid
C 10H 12O 2
cat. Pd (0)
Et 3B (2.4 eq)
Et 3N (1.2 eq)
LiCl (1.0 eq)
THF
rt
3) liq NH 3
CH 3CN
45 °C
4) 250 °C, neat
HO
major
1) CF 3COCH 3, NaHCO 3, Oxone ®
CH 3CN-H 2O, rt, pH7-7.5
2) 5% NaOH aq, MeOH
100 °C, 12 h
1) SOCl 2, benzene;
Et 3N, allyl amine
2) PPh 3, CCl 4
Et 3N, CH 3CN
O
Ph
OMe
H
O 2N
H 2N
+
NC
COOH
88%
N
Bn
CN
OH
CN
minor
O
Ph
OMe

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Fukuyama Group - Group Meeting Problems
08/29/2001
Ph
MeO O
N
O
N
O
Me
N CO2H MeO O
PdI2 (0.2 mol%)
KI (2 mol%)
CO/air (3:1, 600 psi )
MeO
O
Hint: active catalyst = K 2PdI 4
OH
toluene
reflux
1) NBS
30 h, 74%
2) NaH, TsCl
1. TFAA, Py
2. H NH2 NH·HCl
K2CO3, DMF
70 °C
1. CO
Br
2Et
NOH
Na2CO3 2. aq. NaOH, 20 °C
3. 150 °C
A
(C 6H 8O 2)
MeOH
110 °C
3) BuLi, THF
O
A : transient intermediate
Ph
N
–78 °C to rt
4) TMSCl (3 eq.), NaI (3 eq.)
CH 3CN, rt
OH
N
Me
CO 2Me
CN
OH
COCF 3
A
O
O
O
O
CO 2Me
CO 2Me
OMe
CO2Me