Fukuyama Group-Group Meeting Cumulative Examination 4/17/04

1.
Me O Me OH
N
NOCl hν
Me H OH Me H O
pyridine EtOH
H H H H

H H

H. Suginome et al., J. Org. Chem., 54, 5945 (1989)

2.
1) CHBr3, CH2Cl2
aq NaOH (MeCO)2, hν CO2H
phase-transfer cat., 45% 58%
Cl Cl C5H6
2) MeLi (2 eq), –78 to 0 °C 3) Br2, aq NaOH HO2C
Et2O-pentane; 1,4-dioxane, 90%

Michl, J. et al., J. Org. Chem. 53, 4593 (1988)

3.

3) MgX
Ph Ph 1) I(coll)2ClO4
medium toluene, rt OH
OMe
HO membered 86%
O O
CH2Cl2 ring
compound 4) Ca, NH3
–78 °C to rt, 77 % OH
–78 °C, 92%
2) LAH, THF
72%

Y. Kita et al., J. Org. Chem., 61, 7309 (1996)

 1) BH3•THF
4. 2) CH2=C(OMe)Me
OH PPTS
1) AcCl
CO2H ? ?
HO2C
2) EtOH (Compound) 3) NaOEt, EtOH (Compound)
71%
?
(Name)
1) ?
BF3•Et2O O O 2) ? O O
EtO2C I
Et2O 3) ?
100% (Conditions) K. Mori (Olean)

PhI(OAc)2
BzO O 1) ? BzO O I2
OH ?
2) ? hν (Compound)
(Conditions) CN (tungsten lamp)
O
11
S. Hatakeyama (Paeoniflorin)
天然物の全合成, p. 161 and pp. 167-168

5. In the late 1950s R. B. Woodward published his now classic synthesis of the alkaloid reserpine. Woodward
utilized the reaction of 1 (eq. 1) because 3 (eq. 2) was unreactive towards the desired epimerization.

H N H H N H
t-BuCO2H
N N (1)
MeO MeO
H O H O
H H
OMe OMe
O O
1 2

H N H H N H
t-BuCO2H
OAc OAc
N N (2)
MeO MeO
H H H H
MeO2C OMe MeO2C OMe

3 4

A. Provide a general mechanism for the equilibration of 1 to 2. 3-D drawings are not required.

B. Provide clear 3-D drawings of the strating materials and products (1-4). Use them to explain the observed
divergence in reactivity.