Fukuyama Group - Group Meeting Problems Ver.201/10/2006
1

NaNH2 (3.0 eq)
ClOOClOOOA

liq. NH3-Et2O;
NH4Cl

HOA (neat), rt;
NBS, THF-H2O;

1) LiOH, THF-MeOH-H2O
60 °C

t-BuOK, t-BuOH

2) NBS, PPh3, DMF
3) Zn, NH4Cl, EtOH

OHO

HO

E. Nakamura et al., Tetrahedron Lett., 48, 2045 (1992)
D. L. Boger et al., J. Org. Chem., 59, 3453 (1994)

22 ClO4
Ph2C

CPh2

MeO

NEt2
MeO

PhS
MeCN–40 °C, 0.5 hOH

NEt2–40 °C, 0.5 hO

J. Ichikawa et al., J. Am. Chem. Soc., 127, 9696 (2005)

3MeMgI

KOH

I2Et2O–20 °C to rt
30 min; H2O

MeOH, H2O
rt, 3 hr

MeOH
70 °C, 130 min

100%

70%

NBnOONBn
MeO

80%
J. Richard Heys et al., J. Org. Chem., 54, 4702 (1989)

41) LHMDS, hexane
CH2=C(Me)CO2Me–10 °C to rt, 70%O

C15H22O52) O3, CH2Cl2-MeOH–70 °C; Ac2O, Et3N
DMAP, PhH, reflux
60%

C11H16O

1) K2CO3, MeOH, 90%2) p-TsOH·H2O
PhH, reflux, 65%

O

CO2MeA. Srikrishna et al., Tetrahedron Lett., 47, 363 (2006)

5HPhO
NCNOMeH1) TBDMSOTf, CH2Cl2, rt;
MeMgI, Et2O, –78 °C
2) PPTS, CH2Cl2
70% (2 steps)

PhN
MeO
OMe

H. -P. Husson et al., J. Org. Chem., 57, 4211 (1992)

Fukuyama Group - Group Meeting Problems
01/18/2006
1CO2MeMeO

1) EtNO2, t-BuOK 3) SnCl4
t-BuOH, 72%
CH2Cl2, –78 ºCO2) Ac2O, DMAP
Et2O, 79%

tetracycliccompound4) PhH, 60 ºC
92% (2 steps)5) Ra-Ni, H2
MeOH;
HONNaOMe79%

C16H25NO5O

S. C. Denmark et al., J. Org. Chem., ASAP2NHNO

NO2pyrrolidine (2 eq);
PhCHO (0.5 eq);

AcCl (0.5 eq)

Obenzenebenzene/hexane

NCPhN

CNO

90%
M. Ariga et al., J. Org. Chem., 64, 6476 (1999)31) maleic anhydrideneat, 170 °C
90%3) aq. KOH
MeOH, 50 °C
98%2) hν, acetone
28%4) Pb(OAc)4, Py
CH3CN, 55 °C
47%5) AgNO3
MeOH-H2O
98%

S. F. Nelsen et al., J. Am. Chem. Soc., 113, 7882 (1991)
W. G. Dauben et al., J. am. Chem. Soc., 93, 1446 (1971)

4OnBuONHPhO
O n

1 mol % AuCl(PPh3)/AgSbF6Bu

CH2Cl2, rt, 2 hN
H98%PhH

L. Zhang, J. Am. Chem. Soc., 127, 16804 (2005)

51) NaClO2, NaH2PO42-Methyl-2-butene
t-BuOH, H2O, rt

AcO
OHC

HO

H2) MeONa, MeOH, rt;(COCl)2, benzene, rt;
CH2N2, Et2O, 0 °C
77% (2 steps)

Cu(hfacac)2CH2Cl2
reflux

AcOHO

H+H

HOO

H83%2HAcO:O
1J. L. Castro et al., Synthesis, 3398 (2005)

Fukuyama Group - Group Meeting Problems
01/25/2006
11) t-BuLi (1 eq), Et2O;
1,2-dibromoethane (1 eq), 56%
2) NBS (1 eq), MeOH/CH2Cl2

NMe2NTIPS

3) TBAF
4) Boc2O, DMAP, 72% (3 steps)5) Bu Sn,Pd(PPh3), 40%3NBoc*3), 4) Exchange TIPS with Boc, simply.
Snieckus, V. et al., Org. Lett., 4, 815 (2002)21) n-BuLi (1.05 eq)
THF, –78 °C;
TESCl;
s-BuLi (1.2 eq);
MsCl65%3)

OPhClEt3N82%OPrimary AmineHO4) toluene
110 °C;aqueous workup
81%2) NH3, MeOH
40 °C, 15 h(SN2 reaction)
27%PhNH

MeZ only

Danishefsky, S. J. et al., J. Am. Chem. Soc., 126, 6347 (2004)

31)

OO

TMSO

OTMS

BF3·OEt2, CH2Cl2–78 to 10 °C, 3 hr
93%

CO2Me

2) BF3·OEt2, H2O
CH2Cl2, 16 hr
47%

CO2MeO

O
MeO2C

CO2Me

Curran. D. P. et al., J. Org. Chem., 60, 345 (1995)

4OO

ROO

1) TsNHNH2
THF, 50 °C

ORMeO2) Basic Al2O3
CH2Cl2, rt>71% (2 steps)

Me4) TfOH, CH2Cl2rt, 41%TMS

R=1) Me +N
3OHOOH
MeMeOMeOHOH

J. L. Wood et al., J. Am. Chem. Soc., 123, 2097 (2001)

5BnO

3) cat. Rh2(OAc)4
methyl propiolate
PhH, 60 °C, 75%

CO2-NaH, THF, reflux;
H3O+, 92%2) 180 °C, 0.1 mmHg
85%

C13H16O21) Mg
t -Butyl bromoacetate
Et2O, 84%2) KOH, MeOH
24 h; H3O+, quant3) AcOK, Ac2O, rt, 2 h;Δ, 3 h, 93 %O

OBnRosini. G. et al., Org. Lett., 2, 4145 (2000)