Fukuyama Group-Group Meeting Cumulative Examination 04/19/2008

1. Me
Me 1) AuCl (1 mol%)
Me Me
CH2Cl2, 88% Me
Me
2) HCl, MeCN
91% O
OTIPS

S. A. Kozmin et al., J. Am. Chem. Soc., 126, 11806 (2004)

2. n-BuLi (3.0 equiv)

TMP (3.0 equiv)
O O EtMgBr LiCl (6.0 equiv) O
(1.2 equiv) THF, 0 °C; TFA HO
N N O
THF C10H21 CH2Cl2
I
0 °C to rt C10H21
OPMB
(5.0 equiv) 96%
88%
–78 °C to rt

66%, dr = 90:10
S. P. Marsden et al., Synthesis, 3263 (2005)
S. P. Marsden et al., J. Am. Chem. Soc., 129, 12600 (2007)

3. fuming H2SO4
MeCN-hexane
0 °C to rt;
OH
H2O, reflux
O NH2

演習で学ぶ有機反応機構B例題 (化学同人)
E. N. Jacobsen et al., Org. Synth., Coll. Vol. X 29 (2004)

4. 1) Hg(OAc)2
AcOH, 70-75 °C CO2Me
+ AcO
OAc
2) MeO2C CO2Me CO2Me
benzene, reflux

演習で学ぶ有機反応機構C例題 (化学同人)
C. R. Noller and R. Dinsmore, Org. Synth., Coll. Vol. II 358 (1943)

5.
NCS 2) TfOCH2CO2Et 1) mCPBA
benzene; MeCN CH2Cl2
C11H18O2S CO2Et
S MgBr 3) DBU, MeCN 2) C2Cl6, NaH
0 °C DME
THF, 0 °C
E. Vedejs et al., J. Org. Chem., 43, 4831 (1978)
E. Vedejs et al., J. Org. Chem., 43, 4884 (1978)

6. Both products A and B, derived from the same starting material, are tetracyclic compounds, and B is a
regioisomer of A. Provide the structures of A and B, and draw a reasonable arrow-pushing mechanism for
each reaction.

1) TMSCl
imidazole
OMe
DMF OH 1) ICl, THF
A B
2) 140 °C 2) SmI2
xylene THF-HMPA
3) PPTS OAc 0 °C to rt
MeOH
K. Suzuki et al., Angew. Chem. Int. Ed., 45, 6294 (2006)