Chemistry Reference
In-Depth Information
S
S
S
S
BuLi
Bis(3-thienyl)disulfide
BuLi
CuCl
2
S
S
S
S
338
339
19
S
S
S
S
BuLi
CuCl
2
BuLi
Bis(benzenesulfonyl)-
sulfide
S
S
S
S
S
S
340
341
Scheme 86 Synthesis of tetrathienoacene (339) and pentathienoacene (341) starting from
3-bromo-TT (19)[
23
,
135
]
S
S
S
S
Br
BuLi
TIPSCl
S(SnBu
3
)
2
Pd(0)
LDA
56
TIPS
TIPS
TIPS
TIPS
S
S
S
S
S
Br
342
343
344
S
S
S
S
BuLi
CuCl
2
TFA
TIPS
TIPS
S
S
S
S
S
S
345
346
Scheme 87 Synthesis of pentathienoacene 346 using a halogen dance strategy [
134
]
Br
S
S
S
S
S
TIPS
TIPS
LDA
S(SnBu
3
)
2
Pd(0)
271
S
TIPS
S
S
S
S
347
348
S
S
S
S
S
S
S
S
TIPS
TIPS
BuLi
CuCl
2
TBAF
S
S
S
S
S
S
349
350
Scheme 88 Synthesis of heptathienoacene 350 [
134
]
Thienoacenes can also be prepared utilizing alkynes, and an intramolecular
double sulfur-sulfur bonding of a dithienylacetylenedithiolate oxidative work-up
with K
3
[Fe(CN)
6
] forming a 1,2-dithiin. Thermolysis caused extrusion of sulfur and
the formation of 364 [
139
] (Scheme
90
).
Diacetylene 365, possessing
o
-bromothienyl subunits at both ends, underwent an
intramolecular triple cyclization, resulting in pentathienoacene 367 in 22% yield
(Scheme
91
)[
140
,
141
].
