Fukuyama Group - Group Meeting Problems 07/04/2007

1
2
3
4
5
Br
O
O
Fukuyama Group - Group Meeting Problems
07/04/2007
O
Me
N Bn
N
Boc
N 2 O
H
1) O
Cl
O
Et3N, CH2Cl2, 0 °C
2) PTSA
THF/H 2O, Δ
3) NaIO 4, NaHCO 3
CH 2Cl 2
CO 2Me
+ OTIPS
Me 2N
O t Bu
NMe 2
toluene, 100 ºC
87%
O MgBr
CuI
HO
O
HO
OH
THF
–20 ºC to rt
O
85%
O
O
C 14H 15NO 3
C 14H 22N 2O 5
IBX, NMO
DMSO
70 ºC
64%
hν (vycor)
ClCH 2CH 2Cl
rt; reflux
68%
1) In (powder)
Me
Br
THF-aq. NH4Cl 2) MsCl, Et 3N
toluene
sealed tube
rt to 190 °C
43% (2 steps)
H
O
H
N
H
O Bn
Me H
OMs
B. Alcaide et al., Eur. J. Org. Chem., 98 (2005)
1) HCl, NaNO 2
H 2O, 0 ºC
Br
2) H 2, Pd/C
AcOH, Ac 2O
35%, 86% de
(2 steps)
HO
AcHN
O
Me
OTIPS
R. L. Danheiser et al., J. Am. Chem. Soc., 116, 9471 (1994)
N
Boc
CO 2Me
B. Stanovnik et al., Eur. J. Org. Chem., 1581 (1999)
DMAP
formalin
THF
50 ºC
63%
HCl
CH 2Cl 2
0 ºC
68%
C. M. Williams et al., Eur. J. Org. Chem., 3181 (2006)
1) Me2NCH(OMe) 2
dichloroethane, rt;
evaporation;
O
O
Ac2O, 100 ºC, 68% O
O
2) LiHMDS, t-BuOOH
THF, 0 ºC, 77%
OH
O
B. Trost et al., J. Am. Chem. Soc., 121, 6131 (1999)
O
O

1
2
O
OH
CO2H 3
AcO
4
5
Me
OBn
NO 2
Fukuyama Group - Group Meeting Problems
07/17/2007
TMS
C 6H 14Si
OBn
+
O
N 3
CN
S
Et
N 2
O
OBn
CHO
NH
Me
s-BuLi
Ti(Oi-Pr) 4, TMEDA
THF, –78 to –40 °C
OMe
1) A, THF, –78 °C
2) toluene, 100 °C
80% (2 steps)
OMe
1) PMBNH 2
CF 3CH 2OH
70 °C
2) CSA, PhH
56% (2 steps)
O O
Cl Cl
Br Br (1 eq)
Zn (2 eq)
–78 °C to rt
O
72%
TMS
1) copper (ll)∗
tol, reflux
91%
2) K 2CO 3
MeOH
A
C 18H 41O 4LiSiTi
tricyclic
compound
mixture of two
diastereomers
3) hν, THF, 77%
4) n-Bu 4NOH
DMF, –20 °C
49%
Et 3N (excess)
THF-H 2O (10:1)
70 °C
quant.
OBn
OBn
HN
OBn
OH
M. A. Ciufolini et al., Angew. Chem. Int. Ed., 41, 4688 (2002)
toluene
reflux
66%
Cr(CO) 5
Me OMe
dioxane
reflux;
evaporation;
silica gel/CHCl 3
3) KHMDS, THF;
CS 2, MeI
4) n-Bu 3SnH, AIBN
tol, 110 °C
60% (3 steps)
C 19H 22N 2O 3
N CO PMB
2H
O
OH
single isomer
Y. Kobayashi et al., Synlett 1585 (2007)
1) Pd/C, H 2
MeOH, rt;
LAH,THF
0 °C to reflux
48%
2) AcOH
rt
(*epimerization)
N
H
Et
A. Padwa et al., Org. Lett., 7, 2925 (2005)
OH
Me
O
45%
L. Zhang and J. W. Herndon, Heterocycles, 67, 233 (2006)
5) KOH, MeOH
60 °C; HCl;
NaHCO 3, KI
I 2, THF-H 2O
6) TBSOTf
2,6-lutidine
CH 2Cl 2, 0 °C to rt
77% (3 steps)
Me
O
I
O
Me
N
OTBS
∗ bis-(N-t-butylsalicylaldiminato) copper
S. J. Danishefsky et al., J. Am. Chem. Soc., 129, 3498 (2007)

1
2
3
4
5
O
Ph N
O
O
Fukuyama Group - Group Meeting Problems
07/25/2007
O
OTBS
O
O
O
t-BuOK
CHBr 3
68%
1) LDA (2 eq), THF
–78 °C to reflux
2) CCl 4, reflux
72% (2 steps)
1) MeN 3, toluene
rt, 87%
2) hν, dioxane, 78%
3) AcOH-H 2O-THF
55 °C, 67%
+
O O O
1) Cl 3CCOCl (1 eq)
Zn-Cu
ether, reflux, 1 d
2) Zn
H 2O
AcOH, 80 °C, 1 d
(yield not reported)
MeLi, Et 2O, 0 °C to rt;
O N R;
DDQ (aromatization)
40%
C 11H 18O
C 13H 14N 2O 3
+
C 12H 12O
O
N
M. Lechner et al., Angew. Chem. Int. Ed., 14, 765 (1975)
R
1) (CH 3) 3SiCH(CH 3)CO 2Et
LDA, THF, –78 °C to reflux
2) NaOH, EtOH, reflux
75% (2 steps)
3) (COCl) 2, benzene, rt to 55 °C
4) Et 3N, toluene, reflux
31% (2 steps)
5) HI, benzene, 51%
R =
B. B. Snider et al., J. Org. Chem., 53, 4508 (1988)
4) OMe
·
PPTS, rt, 63%
5) hν, MeCN
47% (dr = 4 : 1)
Ph
O
O
O
N
O
OMe
NMe
P. Garner et al., J. Org. Chem., 54, 2041 (1989)
glycine
toluene, reflux
72%
COMe
COMe
L. T. Scott et al., J. Am. Chem. Soc., 119, 10963 (1997)
[Rh(nbd)dppp]PF 6 (5 mol%)
BHT (10 mol%)
m-xylene, 135 °C
81%
Ni(cod) 2 (10 mol%)
PCy 3 (20 mol%)
toluene, 100 °C
89%
Murakami, M. et al. J. Am. Chem. Soc. 124, 13976 (2002)
Murakami, M. et al. Chem. Commun. 4599 (2006)
O
O