Fukuyama Group - Group Meeting Problems
07/04/2007
1N2OBrHOhν (vycor)+OTIPSBrOTIPSClCH2CH2Cl
rt; reflux

MeMe68%R. L. Danheiser et al., J. Am. Chem. Soc., 116, 9471 (1994)

21)
NBn

MeO

Cl

2) PTSATHF/H2O, Δ
3) NaIO4, NaHCO3
CH2Cl2O

HBr

Et3N, CH2Cl2, 0 °C
HO1) In (powder)O

THF-aq. NH4Cl

C14H15NO3

2) MsCl, Et3N
toluenesealed tube
rt to 190 °C

OMs
OHH MeHNO

Bn

43% (2 steps)
B. Alcaide et al., Eur. J. Org. Chem., 98 (2005)

3OtBu
Me2NO

N
Boc

CO2MeNMe2

toluene, 100 ºC

C14H22N2O587%1) HCl, NaNO2
H2O, 0 ºC

AcHN2) H2, Pd/C
AcOH, Ac2O
35%, 86% de(2 steps)

ON
Boc

CO2Me

B. Stanovnik et al., Eur. J. Org. Chem., 1581 (1999)

4OCuI

IBX, NMO

DMAP
formalin

HCl

THF–20 ºC to rt

DMSO
70 ºC

THF
50 ºC

CH2Cl20 ºC

85%64%63%68%

O

MgBrOC. M. Williams et al., Eur. J. Org. Chem., 3181 (2006)

5OHO1) Me2NCH(OMe)2dichloroethane, rt;evaporation;
Ac2O, 100 ºC, 68%O

HOOOHO

2) LiHMDS, t-BuOOH
THF, 0 ºC, 77%OOOOOHOB. Trost et al., J. Am. Chem. Soc., 121, 6131 (1999)

Fukuyama Group - Group Meeting Problems
07/17/2007
s-BuLi
Ti(Oi-Pr)4, TMEDA

1
TMS

A

THF, –78 to –40 °C

C6H14Si

C18H41O4LiSiTi
OBn

OBn

OBnOHOBn
1) A, THF, –78 °C

CHO

tricycliccompound2) toluene, 100 °C
80% (2 steps)

N3OBn3) hν, THF, 77%4) n-Bu4NOH
DMF, –20 °C
49%HNOBnM. A. Ciufolini et al., Angew. Chem. Int. Ed., 41, 4688 (2002)21) PMBNH2
CF3CH2OH
70 °C

O+ CN

OMe 2) CSA, PhH
56% (2 steps)
OMeOH
CO2H

mixture of two
diastereomers

Et3N (excess)
THF-H2O (10:1)
70 °C

PMB CO H
2NO
OH

quant.

single isomer

Y. Kobayashi et al., Synlett 1585 (2007)

3O
Cl

NO2EtS1) Pd/C, H2
MeOH, rt;
LAH,THF
0 °C to reflux
48%

OClBr Br (1 eq)

Zn (2 eq)
NH–78 °C to rt

toluenereflux72%

C19H22N2O366%NH2) AcOH
rt(*epimerization)

N
Et

A. Padwa et al., Org. Lett., 7, 2925 (2005)
Cr(CO)54
TMS

Me5AcOMeN2OOO

MeOMe

dioxanereflux;

Meevaporation;
silica gel/CHCl3

Me45%
L. Zhang and J. W. Herndon, Heterocycles, 67, 233 (2006)

1) copper (ll)∗3) KHMDS, THF;
tol, reflux
CS2, MeI
91%2) K2CO3
MeOH

OH O

4) n-Bu3SnH, AIBN
tol, 110 °C
60% (3 steps)5) KOH, MeOH
60 °C; HCl;
NaHCO3, KI
I2, THF-H2O
6) TBSOTf
2,6-lutidine
CH2Cl2, 0 °C to rt
77% (3 steps)

IOOOTBSMe∗ bis-(N-t-butylsalicylaldiminato) copper
S. J. Danishefsky et al., J. Am. Chem. Soc., 129, 3498 (2007)

Fukuyama Group - Group Meeting Problems
07/25/2007
1t-BuOKO N

MeLi, Et2O, 0 °C to rt;

CHBr3

O N

RR;

R=DDQ (aromatization)

68%

40%
M. Lechner et al., Angew. Chem. Int. Ed., 14, 765 (1975)

21) (CH3)3SiCH(CH3)CO2Et
LDA, THF, –78 °C to reflux
2) NaOH, EtOH, reflux
75% (2 steps)

1) LDA (2 eq), THF–78 °C to reflux
OO2) CCl4, reflux
72% (2 steps)O

C11H18O

3) (COCl)2, benzene, rt to 55 °C4) Et3N, toluene, reflux
31% (2 steps)
5) HI, benzene, 51%

O

B. B. Snider et al., J. Org. Chem., 53, 4508 (1988)31) MeN3, toluene
rt, 87%OTBSOPh4)
C13H14N2O32) hν, dioxane, 78%3) AcOH-H2O-THF
55 °C, 67%

NOOMeOMeO·
PPTS, rt, 63%5) hν, MeCN
47% (dr = 4 : 1)ON

PhNMeO

P. Garner et al., J. Org. Chem., 54, 2041 (1989)

4COMeO+OO

O

glycine+toluene, reflux

O72%

COMe

L. T. Scott et al., J. Am. Chem. Soc., 119, 10963 (1997)

5[Rh(nbd)dppp]PF6 (5 mol%)BHT (10 mol%)
O1) Cl3CCOCl (1 eq)
Zn-Cu
ether, reflux, 1 d2) Zn
H2O
AcOH, 80 °C, 1 d(yield not reported)

m-xylene, 135 °C
81%
C12H12O

Ni(cod)2 (10 mol%)
PCy3 (20 mol%)toluene, 100 °C
89%O

Murakami, M. et al. J. Am. Chem. Soc. 124, 13976 (2002)
Murakami, M. et al. Chem. Commun. 4599 (2006)