Br
Br
OH
OMe
OMe
OH
HO
Br
Br
Br
t-Bu
t-Bu
OH
OMe
OMe
OH
HO
Bu-t
Br
OMe
OMe
OMe
Br
Br
Br
OMe
R
OMe
OMe
OMe
R
R
R
OMe
16a
24
25
23a R = Ph, 67%
23b R = p-MePh, 63%
Br 2
CH 2 Cl 2 , r.t.
(CH 3 ) 2 SO 4 , K 2 CO 3
acetone
72%
92%
K 2 CO 3 , Pd(PPh 3 ) 4 , DMF
B(OH) 2
26a R = H
26b R = CH 3
R
OMe
Br
OMe
R
Scheme 5 Synthesis and reaction of pentabromo-substituted 24
p-substituted-phenol
30
R
R
OH
OH
MeO
OMe
OH
HO
29
OMe
MeO
31a R = t-Bu (54%)
31b R = Ph (78%)
31c R = i-Pr (59%)
R
OH
OMe
MeO
R
OH
OMe MeO
R
OH
OH
HO
R
OH
OH
HO
33a R = t-Bu (90%)
33b R = Ph (95%)
33c R = i-Pr (92%)
32a R = t-Bu (21%)
32b R = Ph (22%)
32c R = i-Pr (20%)
o-dichlorobenzene
29, p-TsOH
BBr 3 , dichloromethane
p-TsOH, toluene
27
OMe
MeO
CHO
OHC
28
OMe
MeO
NaBH 4 , MeOH
hexamethylenamine
CF 3 CO 2 H, reflux
75%
98%
Scheme 6 Synthesis of macrocycles 32–33
6 Triptycene-Derived Macrocyclic Arenes
147