Self-Assembly Processes of Bis(bipyridine)-BINOL Helicates
was washed three times with satd. aq. EDTA, water and brine. The
CD were generated. For ESI-MS and CD studies 5ϫ10–5 mol/L
solutions were prepared (CH Cl /CH CN, 1:1).
organic layer was dried with Na
moved. The crude product was purified by flash column
chromatography on silica gel [n-hexane/EtOAc (3:1) + 5% Et N].
Yield 28 mg (29%); m.p. 138–140 °C. Specific rotation: (P)-3b:
2
SO
4
and the solvents were re-
2
2
3
[Ag
2
{(M)-2}
2
](BF
4
)
2
/[Ag
2
{(P)-2} ](BF : CD: (M): λ (∆ε): = 232
2
4 2
)
3
(
–26.9), 265 (12.3), 333 (–14.3 L/molcm) nm; (P): = 232 (26.5), 266
Cl /CD CN):
, [Ag2] , 1085.5 (10) [Ag2 + H] ,
2
7
–1
(–13.2), 330 (14.8 L/molcm) nm. MS (ESI, pos., CD
m/z (%) = 1139.4 (25) [Ag
1031.6 (10) [2 + H] , 724.0 (15) [Ag2 + 2H] , 570.2 (25) [Ag2 +
2
2
3
[α]
D
= +122.0ϫ10 (c = 0.395, CH
2 2 f
Cl ); R = 0.67 [n-hexane/
2
+
+
2+
2
2
2
]
EtOAc (3:1) + 5% Et
3
N]. MS (ESI, pos.): m/z (%) = 975.5 (70)
+
3+
+
+
[
[
M + H] , 488.2 (100) [M + 2H] . HRMS (ESI, pos.): calcd. for
2
+
2+
1
+
1
H] , 516.3 (100) [2 + 2H]
298.0 K, 500.1 MHz]: δ = 0.87 (t, J31,30 = 7.1 Hz, 12 H, 31-H),
.23–1.40 (m, 32 H, 27-H, 28-H, 29-H, 30-H), 1.64–1.72 (m, 8 H,
2 2 3
. H NMR [CD Cl /CD CN (2:1),
C
66
H
63
N
4
O
4
]
975.4844; found 975.4835. H NMR (CDCl
3
,
3
3
3
1
2
=
(
00.0 K, 500.1 MHz): δ = 0.88 (t,
.23–1.39 (m, 16 H, 27-H, 28-H, 29-H, 30-H), 1.63–1.70 (m, 4 H,
J31,30 = 7.1 Hz, 6 H, 31-H),
1
3
2
3
26-H), 2.27 (s, 12 H, OCH ), 2.73 (t, J25,26 = 7.8 Hz, 8 H, 25-H),
4.27 (d, J = 5.5 Hz, 4 H, OCH
6-H), 2.64–2.71 (m, 4 H, 25-H), 2.67 (s, 6 H, OCH
3
), 4.93 (d, J
O), 5.09 (d, J = 6.2 Hz, 2 H, OCH O), 7.22
d, J8,7 = 8.1 Hz, 2 H, 8-H), 7.34 (dd, J7,6 = 7.4, J7,8 = 8.1 Hz,
2
O), 4.35 (d, 2J = 5.5 Hz, 4 H,
2
2
6.2 Hz, 2 H, OCH
2
2
3
3
3
3
3
OCH
2
O), 7.20 (d, J8,7 = 8.5 Hz, 4 H, 8-H), 7.28 (ddd, J7,8 = 8.5,
3
J =
7,6 = 6.8, J7,5 = 1.2 Hz, 4 H, 7-H), 7.42 (ddd, J6,5 = 8.4, 3J6,7
4
3
3
3
2
H, 7-H), 7.45 (dd, J6,7 = 7.4, J6,5 = 7.4 Hz, 2 H, 6-H), 7.66 (dd,
4
3
3
4
3
6.8, J6,8 = 1.2 Hz, 4 H, 6-H), 7.76 (d, J13,12 = 8.4 Hz, 8 H, 13-H),
7.83 (d, J12,13 = 8.4 Hz, 8 H, 12-H), 7.91 (d, J5,6 = 8.4 Hz, 4 H,
5-H), 7.94 (dd, J22,21 = 8.3, J22,24 = 2.1 Hz, 4 H, 22-H), 7.99 (s,
4
J
22,21 = 8.1, J22,24 = 1.4 Hz, 2 H, 22-H), 7.86 (d, J5,6 = 7.4 Hz,
3
3
3
4
2
H, 5-H), 7.92 (dd, J16,17 = 8.2, J16,19 = 2.1 Hz, 2 H, 16-H), 8.27
3
4
3
3
(s, 2 H, 4-H), 8.34 (d, J21,22 = 8.1 Hz, 2 H, 21-H), 8.41 (d, J17,16
3
3
H, 4-H), 8.28 (d, J21,22 = 8.3 Hz, 4 H, 21-H), 8.34 (dd, J16,17
=
=
=
8.2 Hz, 2 H, 17-H), 8.52 (s, 2 H, 24-H), 8.80 (s, 2 H, 19-H) ppm.
4
3
5
1
3
8.5, J16,19 = 2.2 Hz, 4 H, 16-H), 8.37 (dd, J17,16 = 8.5, J17,19
C NMR (CDCl
3
, 300.0 K, 125.8 MHz): δ = 14.0 (C-31), 22.6 (C-
4
0
.6 Hz, 4 H, 17-H), 8.53 (d, J24,22 = 2.1 Hz, 4 H, 24-H), 8.93 (dd,
3
2
1
0), 29.05, 29.08 (C-28, C-29)*, 31.0 (C-26), 31.7 (C-27), 32.9 (C-
4
19,16 = 2.2, J19,17 = 0.6 Hz, 4 H, 19-H) ppm. 13C NMR [CD
CD CN (2:1), 298.0 K, 125.8 MHz]: δ = 13.6 (C-31), 22.5 (C-30),
8.9 (C-28/C-29), 30.8 (C-26), 31.6 (C-27), 32.4 (C-25), 55.6
OCH ), 98.4 (OCH O), 122.3 (C-17/C-21), 125.4 (C-6), 126.0 (C-
5
J
2 2
Cl /
5), 56.3 (OCH
1), 99.2 (OCH
3
), 77.7, 77.9 (C-12, C-13)*, 79.6 (C-14), 80.1 (C-
O), 115.9 (C-3), 118.6 (C-15), 120.1 (C-17), 121.3
3
2
2
(
(C-21), 125.7 (C-1), 125.9 (C-6), 126.4 (C-8), 127.8 (C-5), 128.0 (C-
3
2
7
2
), 130.1 (C-10), 134.2 (C-9), 136.1 (C-4), 137.1 (C-22), 139.0 (C-
3), 140.2 (C-16), 149.3 (C-24), 152.6 (C-19), 152.7 (C-20), 153.6
8
1
1
), 126.4 (C-1), 126.5 (C-7), 126.9 (C-13), 128.0 (C-5), 130.4 (C-
2), 130.6 (C-4), 130.9 (C-10), 133.6 (C-9), 134.4 (C-3), 134.9 (C-
4), 136.8 (C-16), 137.4 (C-15), 139.0 (C-22), 139.6 (C-11), 140.9
(C-2), 155.4 (C-18) ppm; * assignment may be interchanged.
5
-(Bromoethynyl)-5Ј-heptyl-2,2Ј-bipyridine (15b): Br (22 µL) was
2
(
1
C-23), 148.7 (C-19), 149.5 (C-20), 150.8 (C-24), 150.9 (C-2/C-
8) ppm.
added to a solution of ice (320 mg) and aq. NaOH (130 µL, 10 mol/
L) in an open flask to form a light-yellow solution of sodium hypo-
bromite. A satd. solution of 5-ethynyl-5Ј-heptyl-2,2Ј-bipyridine
[
2
2 4 2 2 4 2
Ag {(M)-3a} ](BF ) /[Ag{(P)-3a} ](BF ) : CD: (M): λ (∆ε) = 237
(
(
6.4), 256 (19.3), 275 (–6.8), 344 (–14.8), 367 (–22.9 L/molcm) nm;
P) = 236 (–7.7), 256 (–19.9), 277 (6.9), 345 (16.3), 368 (24.2 L/
(23b; 100 mg, 0.432 mmol) in THF was slowly added dropwise (it
is crucial to keep the amount of THF as small as possible). The
reaction was monitored by TLC [n-hexane/EtOAC (5:1) + 0.5%
molcm) nm. MS (ESI, pos., CD
2
Cl
, [Ag3a] , 779.3 (100) [3a + H] , 390.1 (50) [3a + 2H]
H NMR [CD Cl /CD CN (5:32), 298.0 K, 500.1 MHz]: δ = 2.61
s, 12 H, OCH ), 4.81 (d, J = 5.9 Hz, 4 H, OCH
.9 Hz, 4 H, OCH
2 3
/CD CN): m/z (%) = 887.2 (90)
2
+
+
+
2+
[
Ag
2
3a
2
]
.
Et
satd. aq. NH
ganic phase was dried with Na
The crude product was purified by chromatography on silica gel
n-hexane/EtOAc (10:1) + 5% Et N]. Yield 127 mg (82%); m.p.
3 °C. 0.67 [n-hexane/EtOAc (10:1) 5% Et N].
21BrN ·1/9C 14 (357.29+9.57): calcd. C 64.39, H 6.20, N
.64; found C 64.55, H 6.21, N 7.67. MS (EI): m/z (%) = 356.1 (100)
3
N]. After about 24 h the reaction was quenched by addition of
Cl. The product was extracted with CH Cl . The or-
SO and the solvent was removed.
1
2
2
3
4
2
2
2
2
(
3
2
O), 4.88 (d, J =
2
O), 7.08 (d, J8,7 = 8.5 Hz, 4 H, 8-H), 7.30 (ddd,
2
4
3
5
3
3
4
3
J
7,8 = 8.5, J7,6 = 6.8, J7,5 = 2.2 Hz, 4 H, 7-H), 7.44 (ddd, J6,7 =
[
3
4
3
6
.8, 3J6,5 = 8.2, J6,8 = 1.1 Hz, 4 H, 6-H), 7.51 (ddd, J23,24 = 4.9,
7
R
f
=
+
3
3
4
3
J
23,22 = 7.9, J23,21 = 1.1 Hz, 4 H, 23-H), 7.87 (d, J5,6 = 8.2 Hz,
H, 5-H), 7.99 (ddd, J22,23 = 7.9, J22,21 = 7.9, J22,24 = 1.7 Hz, 4
H, 22-H), 8.09 (dd, J
C
19
H
2
6
H
3
3
4
4
7
3
4
7
9
+
81
+
79
+
= 8.4, J
= 2.1 Hz, 4 H, 16-H), 8.25–
[M( Br)] , 358.1 (99) [M( Br)] , 285.0 (38) [M( Br) – C
5
+
H
11] ,
16,17
16,19
3
4
81
+
79
8.30 (m, 12 H, 4-H, 17-H, 21-H), 8.64 (ddd, J
= 4.9, J
24,22
=
=
2
85.0 (38) [M( Br) – C
5
+
H
11] , 271.0 (98) [M( Br) – C
6
H
H
13] , 273.0
24,23
5
4
5
81
79
+
24,21
1.7, J = 0.8 Hz, 4 H, 24-H), 8.74 (dd, J
= 2.1, J
(98) [M( Br) – C
6
H
13] . HRMS (EI): calcd. for [C19
21 BrN
298.0 K,
), 1.22–1.38 (m, 8
2
]
19,16
19,17
1
3
1
0.6 Hz, 4 H, 19-H) ppm.
2 2 3
C NMR [CD Cl /CD CN (5:3),
3
4
56.0888; found 356.0896.
00.1 MHz): δ = 0.87 (t, J = 7.1 Hz, 3 H, CH
H
NMR (CDCl
3
,
3
298.0 K, 125.8 MHz]: δ = 56.6 (OCH ), 77.3 (C-13)*, 78.8 (C-14),
3
3
3
79.2 (C-12)*, 81.4 (C-11), 99.6 (OCH O), 115.9 (C-3), 120.6 (C-
2
H, 4 CH
CH -bipy), 7.62 (dd, J = 8.1, J = 2.2 Hz, 1 H, bipy), 7.83 (dd, J
8.3, J = 2.1 Hz, 1 H, bipy), 8.29 (d, J = 8.1 Hz, 1 H, bipy),
2
), 1.60–1.69 (m, 2 H, CH
2
), 2.65 (t, J = 7.6 Hz, 2 H,
3
4
3
15), 122.2 (C-17), 123.3 (C-21), 126.10, 126.12 (C-1/C-23), 126.58,
2
4
3
126.61 (C-6/C-8), 128.6 (C-5), 128.8 (C-7), 130.7 (C-10), 134.8 (C-
9), 136.9 (C-4), 139.3 (C-22), 142.2 (C-16), 151.2 (C-24), 152.6 (C-
20), 152.9 (C-18), 153.75 (C-2), 153.81 (C-19) ppm; * assignments
may be interchanged.
=
8
3
5
4
.34 (dd, J = 8.3, J = 0.7 Hz, 1 H, bipy), 8.49 (d, J = 2.2 Hz, 1
4
5
13
H, bipy), 8.49 (dd, J = 2.1, J = 0.7 Hz, 1 H, bipy) ppm. C NMR
(
(
(
CDCl
CH ), 29.2 (CH
Br-CϵC-bipy), 77.5 (Br-CϵC-bipy), 119.5 (bipy), 120.1 (bipy),
3
, 298.0 K, 100.6 MHz): δ = 14.2 (CH
3
), 22.8 (CH
2
), 29.2
2
2
), 31.2 (CH ), 31.9 (CH ), 33.0 (CH
2
2
2
-bipy), 52.3
Supporting Information (see also the footnote on the first page of
2 2 4 2
this article): MS spectra of the complexes [Ag 3a ](BF ) and
1
1
21.2 (bipy), 136.9 (bipy), 138.9 (bipy), 139.9 (bipy), 149.6 (bipy),
52.2 (bipy), 153.1 (bipy), 155.6 (bipy) ppm.
[
Fe ](BF , CD spectra of both enantiomers of 3a and their sil-
2
2
3
4 4
)
ver(I) helicates.
Preparation of Metal Complexes as Exemplified for the Synthesis of
[
[
(
Ag
Ag(CH
0.6 mL) and CD
2
{(M)-2}
2
](BF
4
)
2
: Compound (M)-2 (3.00 mg, 2.91 µmol) and
(1.065 mg, 2.91 µmol) were dissolved in CD Cl
3
CN (0.3 mL), respectively. The two solutions
CN)
2
]BF
4
2
2
Acknowledgments
3
were combined and mixed. The resulting light-yellow solution was
transferred into an NMR tube. Likewise solutions for ESI-MS and
Financial support from the Deutsche Forschungsgemeinschaft
(DFG) (SFB 624) is gratefully acknowledged.
Eur. J. Org. Chem. 2009, 3885–3894
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3893