Fukuyama Group - Group Meeting Problems 09/05/2001

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Fukuyama Group - Group Meeting Problems
09/05/2001
O O
O
Br
OAc
CO 2Me OBn
N 2
Br
N
Ph
n-Bu CO 2Et
Br Br
O
1) NaCN, DMSO, 130 °C
2) 0.5 mol% [Rh(CO) 2Cl] 2
toluene, 110 °C, 30 min
93%
LTA (1.5 eq)
CO (105 atm)
O
OH
benzene, 80 °C
63%
O
Cu powder
PhH
reflux
3.5 h
t-BuLi (5.5 eq), Et 2O, –78 °C;
TMEDA, –78 °C to rt;
t-BuLi (4 eq)
CO 2Et
THF
–78 °C
PhCOCOPh
1N HCl
THF
65 °C
1 h
A
1) A
THF, –78 °C
2) H + (silica gel)
benzene, reflux
O
O
H
N
Ph
+
BnO
OH
Ph
Ph
OH
O
9 : 1
H
n-Bu
CO 2Et
O

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Fukuyama Group - Group Meeting Problems
09/12/2001
F 3C CF 3
H H
Cl
O Cl
MeO 2C
MeO 2C
O
O
OH
OH
HFIP TFE
·
F 3C
CH 2N 2, Et 2O
0 °C, 2 h;
evap;
n-BuLi
THF, –78 °C, 20 min;
then
cyclopentadiene (10 eq*)
Et 3N (3 eq*)
TFE /Et 2O (1 : 1)
–78 °C to rt
OH
N
H
TFE = trifluoroethanol
OH
O
CF 3CO 3H (8eq*)
CF 3CO 2H, CH 2Cl 2
*
HN
Bn
CO2Me Bu
O
N
O
–78 °C to –30 °C, 1 hr;
then HCl / HFIP-TFE
–78 °C to rt
C 13H 13ClO
74%
(two isomer 10.4 : 1)
R
HO
1) LAH, Et 2O, 0 °C
2) KH (5 eq*), THF
0 °C to rt
*
OH
O
1. propargyl alcohol
PhI(OAc) 2, CH 3CN
+
MeO2C Bu
O
78% (86%ee)
2. Ph3SnH, Et3B toluene
3. 1 M HCl, Et OH
2O O
O
benzoic acid, benzene
reflux, 10 hr
R=
CHO
N
H
79%
Bn
N
O
H H
H CHO
O
R
CO2Me 76% (2 steps)
CO 2Me

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Fukuyama Group - Group Meeting Problems
09/19/2001
O
P
Me
OH
NO 2
Br
NO 2
CO 2Et
H
N
H
CO 2H
NHCbz
OCH 3
CO 2Me
1) COCl 2, DMAP, DMF
25 °C, 1 hr
2) NH 2CH 2CH 2NH 2, DMAP
CH 2Cl 2, 25 °C, 1 hr
3) hν (lamp equipped with pyrex filter)
THF
tert-BuLi;
Li
1) acetone, Ac 2O
ZnCl 2, 48%
2)
PPh3Br n-BuLi, Et2O 85%
1) PhI(OAc) 2
CF 3CH 2OH
CH 3
2) NaHCO 3, MeOH
0 °C to rt
54% (2 steps)
i-PrO
i-PrO
O
O
; aq NH 4Cl
1) SnCl 4, toluene, –78 °C;
NaHCO 3, toluene, 80 °C
2) H 2, RaneyNi, MeOH
160 psi, rt
C 12H 18O 2
;
3) MeMgBr, CuI (cat.)
60%
4) PhI(OAc) 2, I 2
CH 2Cl 2, 80 %
HN NH
H
HO
O
O
i-PrO
i-PrO
OH H
Me
O
H
NH
1) DIBAL, CH 2Cl 2
72%
2) (COCl) 2, DMSO
Et 3N, THF, 68%
3) DBU, CH 2Cl 2
89%
O
HO
O
CH 3
P
H
N H
AcO Cbz
CO 2Me
NO 2
N
H
CHO

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Fukuyama Group - Group Meeting Problems
09/26/2001
O
O
MeO
H 3C
O
OAc
CH 3
N 3
CHO
C CCH2OTBS O NMe
N
N 3
I
NH 2 p-Cl-C 6H 4CHO
CH 3
N
CO 2Me
cat. AcOH
EtOH , reflux
1) PPh 3, THF;
NaBH 4, MeOH, rt
2) I 2, CH 2Cl 2, Et 2O, rt
AgOTf
CH 3CN, 70 °C;
BnMe 3NCN
rt
OAc
O
O
O
MeO
N
40%
OTBS
NMe
1) PMe3 , Toluene , rt;
Ph2C=C=O 2) Pd/C , Toluene,
p-Cl-C6H4 N
reflux N Ph
1) Eu(fod) 3 (10 mol%), toluene, 80 °C, 36 h, 84%
2) hν, Corex, 19 h, 79%
3) LiDBB, THF, –78 °C to 10 °C, 35 h, 57%
LiDBB; lithium di-tert-butylbiphenylide
1) MCPBA
2) (CF 3CO) 2O;
aq. Na 2CO 3
N
OH
H 3C
H 3C
N
H
H
HO CH3
O
H
CH 3
O