Fukuyama Group-Group Meeting Cumulative Examination 07/26/2008

1. 1) SO2Cl2
MT-sulfone CHCl3, reflux
n-C6H13 Me Bu3P=CHCN 99% OH
C17H28O2S2
OH benzene 2) AgNO3 n-C6H13 Me
120 °C MeCN-H2O
81%
72% 3) LAH
THF, 0 °C
T. Tsunoda et al., Tetrahedron Lett., 36, 2531 (1995)

2. 1) ClO2S N · O Br
10 °C; 1) TBAF, rt, 57%
NaHCO3, NaHSO3 NaOH aq. 2) CBr4, Ph3P
H2O, –20 °C, 62% Et4NBr rt, 64% H
OAc bicyclic
compound H H
2) (4 eq.) 91% 3) n-Bu3SnH, AIBN N
toluene, reflux O
OTBS
41%
n-BuLi (4 eq.)
CuI (2 eq.)
THF, –30 °C, 54%
J. D. Kilburn et al., Tetrahedron Lett., 41, 10347 (2000)
S. J. Mickel et al., Org. Synth., 64, 135 (1987)

3. NHTs
1) TsNHNH2 OH
Et2O
O
2) NaH N
DMF, 120 °C H Ts
O
演習で学ぶ有機反応機構C006 (化学同人)
S. H. Kim and P. L. Fuchs, Tetrahedron Lett., 37, 2545 (1996)

4.
Me
Li Cl
HgCl2 (cat.) O Me
Me Me
Et2O Me
Me SMe H2O
–78 to 20 °C Me Me

演習で学ぶ有機反応機構C037 (化学同人)
S. Julia et al., J. Chem. Soc., Chem. Commun., 3, 10 (1974)

5.
1) MeMgI, Et2O, 0 °C isoamyl nitrite H
2) HClO4 aq., 0 °C TiCl4, DTBMP CO2Me
bicyclic
compound N
O 3) methyl acrylate CH2Cl2 O
hydroquinone (cat.) –45 to –15 °C Me
4) LDA, TMSCl
THF, –78 °C

A. Zakarian et al., J. Am. Chem. Soc., 128, 5356 (2006)

6.

CO2Me
Br I
Cp2Zr(Me)Cl (1 eq) dimethyl malonate CO2Me
t-BuLi (2 eq) K2CO3, 18-crown-6
N A
THF, –78 °C to rt; benzene N
evaporation;
I2 (2.5 eq), CH2Cl2

NMe2
1) DBU I
benzene
50 °C

2) H2C=NMe2 I N
CH3CN
50 °C

S. L. Buchwald et al., J. Am. Chem. Soc., 116, 11797 (1994)