Geier and Grindrod
Cl , ꢀ
Refin ed Syn th esis of 2,2′-Bip yr r ole (3).14 To a 500 mL
flask were added 2 (1.72 g, 12.8 mmol) and diglyme (200 mL).
Argon was continuously bubbled through the solution, and the
mixture was heated to ∼60 °C to dissolve 2. To the solution
was added 10% palladium on carbon (1.70 g, 1.60 mmol of
palladium). The mixture was heated to reflux, and monitored
by GC/MS at 15 min intervals (Supporting Information). After
afford rust-red crystals with a metallic luster. λabs (CH
2
2
-3
× 10 ) 343 (39.3), 404 (91.0), 519 (21.7), 662 (137), 812 (14.9),
1
1083 (13.1); H NMR (Supporting Information); LD-MS obsd
+
+
1106.3 (M ); HRMS (FAB) obsd 1107.5021 (MH ), calcd
+
1107.4863 (MH ) (C78
,10,19,24,29,38-H e x a k is (p e n t a flu o r o p h e n y l)[34]-
octa p h yr in (1.1.1.0.1.1.1.0) (4c). The reduction of 1c (140 mg,
58 8
H N ).
5
1
h of reflux, the hot reaction mixture was passed through a
0
.200 mmol) was followed by condensation with 3 (26.4 mg,
.200 mmol) in the presence of Dy(OTf) (0.488 g, 0.800 mmol)
Cl (80 mL) for 25 h at room temperature, addition of
triethylamine (0.56 mL, 4.0 mmol), and oxidation with DDQ
227 mg, 1.00 mmol dissolved in toluene (5 mL)] at room
temperature for 1 h. The entire reaction mixture was filtered
through a pad of silica gel and eluted with CH Cl . The dark
fluted filter. The collected palladium on carbon was washed
with ∼100 mL of hot ethyl acetate. The lavender solution was
evaporated to dryness, and the gray residue was gently rinsed
with three portions of hexanes (10 mL) to wash away residual
diglyme. The crude 3 was purified by sublimation (90 °C, 200
mTorr) to afford an off-white powder (1.28 g), followed by
crystallization from diethyl ether/hexanes to afford a white
crystalline solid [1.2 g, 71%, mp 189-190 °C (lit mp 189-190
0
3
in CH
2
2
[
2
2
green band of HpFPO eluted quickly. The fractions containing
HpFPO were concentrated to dryness. Without further puri-
1
4
°
C) ]. Anal. Calcd for C
8 8 2
H N : C, 72.70; H, 6.10; N, 21.20.
fication, HpFPO was crystallized from CH
afford a maroon powder (25 mg, 16%). λabs (CH
43 (39.3), 404 (91.0), 519 (21.7), 662 (137), 812 (14.9), 1083
2 2
Cl /methanol to
Found: C, 72.76; H, 6.16; N, 21.27. Analytical data are
-3
2
Cl
2
, ꢀ × 10
)
1
6
consistent with literature values. The 2,2′-bipyrrole was
stored in the dark at -15 °C to avoid decomposition.
Gen er a l P r oced u r e for th e P r ep a r a tive-Sca le Syn th e-
ses of [34]Octa p h yr in (1.1.1.0.1.1.1.0), Given for 5,10,19,-
3
1
(13.1); H NMR [CDCl
3
] δ 5.28 (d, J ) 3.8 Hz, 4H), 6.25 (d, J
)
4.8 Hz, 8H), 6.36 (d, J ) 4.8 Hz, 4H), 12.9 (br s, 4H); LD-
+
+
MS obsd 1589.7 (M ); HRMS (FAB) obsd 1591.1400 (MH ),
2
4,29,38-Hexa p h en yl[34]Octa p h yr in (1.1.1.0.1.1.1.0) (4a ).
The reduction of 1a (215 mg, 0.500 mmol) with NaBH (946
mg, 25.0 mmol) in THF/methanol (40 mL, 3:1) afforded the
+
calcd 1591.1410 (MH ) (C74
20 30 8
H F N ). Anal. Calcd for
: C, 55.87; H, 1.27; N, 7.04. Found: C, 56.23; H,
4
74 20 30 8
C H F N
1
.58; N, 7.30.
1
9
corresponding carbinol 1a -OH. The carbinol was dried under
vacuum for 30 min and then immediately subjected to con-
densation with 3 (66.0 mg, 0.500 mmol) in the presence of Yb-
Ack n ow led gm en t. This research was supported by
(
OTf)
3
(1.24 g, 2.00 mmol) in CH
2
Cl
2
(200 mL) at room
an award from Research Corporation. Partial support
for this work was provided by the National Science
Foundation’s Course, Curriculum, and Laboratory Im-
provement Program under Grant DUE-0088227. We
thank Tim LeSaulnier for the preparation of 1c and the
Research Council of Colgate University for a publication
grant. High-resolution FAB mass spectra were obtained
at the Mass Spectrometry Laboratory for Biotechnology
at North Carolina State University. Partial funding for
the facility was obtained from the North Carolina
Biotechnology Center and the NSF.
temperature. The reaction was monitored spectrophotometri-
cally at 15 min intervals. At a reaction time of 50 min,
triethylamine (1.39 mL, 10.0 mmol) was added, followed by
oxidation with p-chloranil (615 mg, 2.50 mmol) at reflux open
to air for 45 min. The entire reaction mixture was filtered
through a pad of silica gel and eluted with CH
moving blue pigment was allowed to elute, and then the
solvent was changed to CH Cl /ethyl acetate (25:2). The dark
green band of HPO eluted quickly. The fractions containing
HPO were concentrated to dryness. The HPO sample was
redissolved in CH
concentrated, and purified by chromatography [silica, CH
and then CH Cl /ethyl acetate (25:1)]. The green band contain-
2 2
Cl . A fast-
2
2
2
Cl
2
(50 mL), adsorbed onto silica gel (6 g),
2
Cl
2
,
2
2
Su p p or tin g In for m a tion Ava ila ble: General experimen-
tal methods; synthesis of 2,2′-(1′-pyrrolinyl)pyrrole 2, descrip-
tion of analytical-scale reactions of 2 leading to 2,2′-bipyrrole
ing HPO was collected, concentrated, and dried under vacuum,
affording HPO (64 mg, 25%) that was subsequently crystallized
from CH
metallic luster. λabs (CH
5
2 2
Cl /methanol to afford rust-red crystals with a
3
, and GC/MS monitoring of reactions of 2 leading to 3;
-
3
2
Cl
2
, ꢀ × 10 ) 340 (38.9), 397 (81.9),
discussion of the calculations for the spectrophotometric
determination of the yield of octaphyrin and corrole; experi-
mental details pertaining to the survey of catalyst conditions,
reaction time course experiments, examination of oxidation
conditions leading to HPO, and stability experiments; GC data
from the refinement of the synthesis of 3; plots of the yield of
HPO as a function of acid concentration and of oxidant
quantity and plots of the yield of HPO or HpFPO as a function
of time; discussion of TLC analysis of 4a ,b; and UV-vis, LD-
1
18 (18.9), 661 (133), 810 (12.8), 1083 (12.4); H NMR (Sup-
+
porting Information); LD-MS obsd 1050.1 (M ); HRMS (FAB)
+
+
obsd 1051.4299 (MH ), calcd 1051.4237 (MH ) (C74
,24-Dip h en yl-10,19,29,38-t et r a k is-(4-m et h ylp h en yl)-
34]octa p h yr in (1.1.1.0.1.1.1.0) (4b). The reduction of 1b (229
.500 mmol) followed by condensation with 3 (66.0 mg, 0.500
mmol) in the presence of Yb(OTf) (1.24 g, 2.00 mmol) in CH
Cl (200 mL) for 40 min at room temperature, addition of
triethylamine (1.39 mL, 10.0 mmol), oxidation with p-chloranil
615 mg, 2.50 mmol) at reflux for 45 min, and purification
identical to the general procedure afforded 4b (65 mg, 23%)
that was subsequently crystallized from CH Cl / methanol to
50 8
H N ).
5
[
0
3
2
-
2
1
MS, and H NMR spectra of octaphyrins 4a -c. This material
(
is available free of charge via the Internet at http://pubs.acs.org.
2
2
J O049131Z
6
412 J . Org. Chem., Vol. 69, No. 19, 2004