Inorganic Chemistry
Article
3
2
COOCH ), 4.07 (s, 1H, N CH), 4.10 (s, 6H, pyOCH ), 4.42 (s, 2H,
2.50 Hz, 1H, CCH), 2.72 (d, J = 12.25 Hz, 2H, CH H ), 2.98 (d,
H,H ax eq
3
3
7
9
3
ar
2
4
N CH py), 4.84 (s, 1H, C H), 4.99 (s, 1H, N CH), 7.00 (br, 2H, H ),
.50 (s, 1H, H ), 7.67 (m, 1H, H ), 7.80 (m, 2H, H ), 8.29 (m, 2H,
H ), 8.86 (m, 1H, H ), 9.00 (m, 1H, H ). HR-ESI (pos): [M + H]
calcd 578.261 47, obsd 578.261 57.
J
= 12.63 Hz, 2H, CH H ), 3.29 (d, JH,H = 2.15 Hz, 2H,
2
H,H
7
ax eq
ar
ar
ar
3
7
N CH CCH), 3.83 (s, 6H, COOCH ), 4.76 (s, 2H, N CH), 7.22 (dd,
2
3
ar
ar
ar
+
3
4
3
ar
3
JH,H = 7.33 Hz, J = 4.93 Hz, 2H, H ), 7.78 (td, J = 7.67 Hz,
H,H H,H
ar
3
ar
JH,H = 1.58 Hz, 2H, H ), 8.10 (d, J = 7.83 Hz, 2H, H ), 8.50 (d,
H,H
Hemiaminal 10 (C H N O , M = 591.61 g/mol). (p-MeO)Npy
3J
ar 13
3
0
33
5
8
W
2
= 4.80 Hz, 2H, H ). C NMR (50 MHz, CDCl ): δ = 43.28,
H,H
3
P2 (1.27 g, 2.86 mmol, 1.0 equiv) was suspended in 20 mL of THF
and heated to 50 °C. At this temperature were added (4-
methoxypyridin-2-yl)methanamine 7 (0.47 g, 3.43 mmol, 1.2 equiv)
and an aqueous solution of formaldehyde (37 wt %, 0.56 g, 0.51 mL,
4
1
4
4
5.57, 50.71, 52.47, 57.61, 62.11, 73.70, 74.06, 122.98, 123.57, 136.41,
49.21, 158.79, 168.32, 203.01. HR-ESI (pos): [M + H] calcd
63.198 14, obsd 463.197 36; [M + Na] calcd 485.180 09, obsd
85.179 46; [M + K] calcd 501.154 03, obsd 501.153 41. Elemental
+
+
+
6
.86 mmol, 2.4 equiv) to the mixture, and the mixture was heated to
1
analysis: [M + / H O] calcd C, 63.68; H, 5.77; N, 11.88; obsd C,
2
2
reflux for 1 h. After the mixture was cooled to ambient temperature,
the solvent was removed in vacuo. The residue was taken up in
methanol. The solvent was allowed to slowly evaporate at ambient
temperature. After several days a white precipitate formed. The
monoesterificated hemiaminal was obtained as the pure product in a
yield of 13.3% (0.23 g, 0.38 mmol). H NMR (200 MHz, CDCl ): δ =
6
3.26; H, 6.10; N, 11.54.
Bispidine B16 (C H N O , M = 464.51 g/mol). Bispidone B15
25
28
4
5
W
(
0.43 g, 0.93 mmol, 1.0 equiv) was suspended in 30 mL of a 3:1
mixture of 1,4-dioxane/aqua dest at −6 °C, and sodium borohydride
(17.8 mg, 0.47 mmol, 0.5 equiv) dissolved in an additional 10 mL of a
3:1 mixture of 1,4-dioxane/aqua dest was added over 15 min. The
reaction mixture was stirred for 2.5 h at −6 °C and another 20 h at 0
C. Then concentrated sulfuric acid was added to adjust the pH to 1.
After the mixture was stirred for 3.5 h at ambient temperature, the pH
was adjusted to 12 by adding an aqueous solution of sodium hydroxide
1
3
3
2
7
2
.30 (s, 3H, N CH ), 2.77 (d, J = 12.38 Hz, 1H, N CH), 2.91 (d,
3 H,H
2
7
2
7
JH,H = 12.25 Hz, 1H, N CH), 3.19 (d, J = 12.00 Hz, 1H, N CH),
.19 (s, 1H, N CH), 3.60 (d, J = 12.38 Hz, 1H, N CH), 3.61 (s,
H, COOCH /pyOCH ), 3.65 (s, 3H, COOCH /pyOCH ), 3.87 (d,
JH,H = 15.00 Hz, 2H, N CH py), 3.93 (s, 3H, COOCH /pyOCH ),
H,H
°
3
2
7
3
H,H
3
3
3
3
3
2
7
2
3
3
(
20 wt %) and the mixture was stirred for another 3 h. 1,4-Dioxane
3
3
4
=
.10 (s, 3H, COOCH /pyOCH ), 5.07 (s, 1H, N CH), 6.71 (dd, J
3 3 H,H
was evaporated from the reaction mixture in vacuo. The aqueous
solution was decanted from solid material and diluted with further 50
mL of aqua dest and extracted with DCM (6 × 50 mL). The combined
organic phases were dried over Na SO , filtered, and concentrated in
vacuo. The residue was recrystallized from acetonitrile, filtered, and
washed with a little amount of acetonitrile to afford the pure product
in a yield of 36.6% (0.16 g, 0.34 mmol). H NMR (200 MHz, CDCl ):
δ = 2.01 (s, 3H, N CH ), 2.23 (t, J = 2.40 Hz, 1H, CCH), 2.46 (d,
JH,H = 5.56 Hz, 1H, C OH), 2.58 (s, 4H, N CH ), 3.25 (d, J
5
5
3
5.37 Hz, J = 1.96 Hz, 1H, H ′), 6.81 (d, J = 5.00 Hz, 1H,
H,H
H,H
6
5 3 3
H ′), 7.13 (d, J = 2.10 Hz, 1H, H ′), 7.21 (dd, J = 7.07 Hz,
H,H
H,H
5
5
5
3
J
= 2.27 Hz, 1H, H ′), 7.41 (d, J = 2.40 Hz, 1H, H ′), 7.48 (br.
H,H
H,H
3 3 6 3
2
4
s, 1H, H ′), 8.18 (d, J = 5.68 Hz, 1H, H ′), 8.43 (br. d, J = 5.56
H,H
H,H
5
3
6
13
Hz, 1H, H ′), 8.68 (d, J = 7.07 Hz, 1H, H ′). C NMR (50 MHz,
H,H
CDCl ): δ = 41.01, 52.34, 52.53, 52.71, 54.66, 55.05, 55.16, 56.74,
1
3
3
5
1
1
7.59, 63.26, 69.61, 72.53, 101.88, 108.01, 108.28, 108.54, 108.94,
10.05, 110.46, 141.82, 149.58, 150.71, 152.59, 158.51, 159.44, 166.42,
66.52, 170.41, 171.38, 173.09.
3
4
3
H,H
3
9
7
4
=
2
H,H
7
2
.53 Hz, 2H, N CH CCH), 3.68 (s, 6H, COOCH ), 4.14 (s, 2H,
2
3
Bispidine B14 (C H N O S, M = 486.58 g/mol). Bispidine B11
2
4
30
4
5
W
3
3
9
3
N CH), 4.85 (d, J = 5.56 Hz, 1H, C H), 7.19 (ddd, J = 7.48
Hz, J = 4.95 Hz, J = 1.26 Hz, 2H, H ), 7.74 (td, J = 7.64
Hz, J = 1.77 Hz, 2H, H ), 7.98 (br d, J = 7.96 Hz, 2H, H ),
H,H
H,H
(
289.3 mg, 0.61 mmol, 1.0 equiv) was dissolved in 10 mL of dry THF
3
4
ar
3
H,H
H,H
H,H
under an atmosphere of argon at 0 °C. Then triphenylphosphine (0.24
g, 0.92 mmol, 1.5 equiv), DIAD (0.186 g, 0.182 mL, 0.92 mmol, 1.5
equiv), and thioacetic acid 11 (0.056 g, 0.05 mL, 0.73 mmol, 1.2
equiv) were subsequently added. The suspension was stirred at 0 °C
overnight while slowly allowing warming to ambient temperature (ice
bath using Dewar). Then 50 mL of aqua dest was added to the
suspension, and it was acidified with concentrated sulfuric acid to pH
4
ar
3
ar
H,H
H,H
3
4
4
ar
8
.47 (ddd, J = 4.89 Hz, J = 1.74 Hz, J = 0.82 Hz, 2H, H ).
H,H H,H H,H
13
C NMR (50 MHz, CDCl ): δ = 43.76, 46.74, 47.58, 52.10, 52.84,
2.12, 73.16, 74.77, 78.96, 122.64, 123.20, 136.23, 148.51, 160.03,
72.34. HR-ESI (pos): [M + H] calcd 465.213 80, obsd 465.213 21;
M + Na] calcd 487.195 74, obsd 487.195 48. Elemental analysis: [M
3
7
1
[
+
+
+
CH CN] calcd C, 64.14; H, 6.18; N, 13.85; obsd C, 64.00; H, 6.22;
2
. The mixture was extracted with DCM (2 × 50 mL). The aqueous
3
N, 13.84.
phase was basified with an aqueous solution of sodium hydroxide (20
wt %) to pH 14 and then extracted with DCM (3 × 50 mL). The
organic phase was dried over Na SO , filtered, and concentrated. The
II
[
Cu (B4)](ClO ) (C H Cl CuN O , M = 838.06 g/mol). A
4 2 30 33 2 5 15 W
solution of copper(II) perchlorate hexahydrate (74.11 mg, 0.2
mmol, 1.0 equiv) in 2.5 mL of acetonitrile was poured into a
suspension of ligand B4 (115.12 mg, 0.2 mmol, 1.0 equiv) in 2.5 mL of
acetonitrile. The resultant blue solution was stirred at ambient
temperature overnight and afterward subjected to ether diffusion. Dark
blue/violet crystals were obtained in a yield of 84.0% (147.4 mg, 0.168
mmol). HR-FAB (pos): [B4 + H O + Cu ] calcd 656.1782, obsd
56.1790. Elemental analysis: [B4 + Cu(ClO ) + 3H O] calcd C,
0.39; H, 4.41; N, 7.85; obsd C, 40.89; H, 4.35; N, 7.95. UV−vis
CH CN, rt), λ [nm]: 629 (λ ), 941. CV (CH CN, rt): E
2
4
orange oil was recrystallized from acetonitrile overnight to afford a
white solid as the pure product in a yield of 27.9% (83.1 mg, 0.17
mmol). H NMR (400 MHz, CDCl ): δ = 1.96 (s, 3H, NCH ), 2.49
1
3
3
2
2
(
d, 2H, J = 12.05 Hz, CH H ), 2.63 (d, 2H, J = 12.05 Hz,
H,H ax eq H,H
3
3
CH H ), 2.70 (t, J = 6.02 Hz, 2H, CH ), 2.83 (t, J = 6.02 Hz,
H, CH ), 3.72 (s, 6H, COOCH ), 4.16 (s, 2H, CH), 4.87 (d, J =
.52 Hz, 1H, C HOH), 7.16 (dd, J = 6.96 Hz, J = 5.46 Hz, 2H,
H ), 7.76 (td, J = 7.69 Hz, J = 1.57 Hz, 2H, H ), 8.15 (d, J
8.16 Hz, 2H, H ), 8.48 (d, J = 4.27 Hz, 2H, H ). C NMR
100 MHz, CDCl ): δ = 35.79, 43.70, 48.97, 52.20, 52.80, 57.58,
2.63, 74.69, 122.74, 123.37, 136.26, 148.63, 159.82, 172.41. HR-ESI
pos): [M] calcd 486.193 69, obsd 486.193 22. Elemental analysis:
M + H O] calcd C, 57.13; H, 6.39; N, 11.10; obsd C, 56.96; H, 6.25;
N, 10.98.
Bispidine B15 (C H N O , M = 462.50 g/mol). Npy P1 (3.50 g,
.13 mmol, 1.0 equiv) was suspended in 50 mL of THF and heated to
0 °C. At this temperature were added propargylamine 12 (0.50 g,
.58 mL, 9.13 mmol, 1.0 equiv) and an aqueous solution of
formaldehyde (37%, 1.48 g, 1.36 mL, 18.26 mmol, 2.0 equiv). The
mixture was heated to reflux for 1.5 h. After the mixture was cooled to
ambient temperature, the solvent was removed in vacuo and the
resulting residue was taken up in methanol. A tan-colored precipitate
formed which was filtered and washed with cold methanol. The pure
product was obtained in a yield of 19.9% (0.84 g, 1.82 mmol). H
NMR (200 MHz, CDCl ): δ = 2.04 (s, 3H, N CH ), 2.23 (t, J =
ax eq
H,H
2
H,H
I
+
3
2
5
2
2
3
H,H
9
3
3
6
4
4 2 2
H,H
H,H
ar
ar
3
4
3
H,H
ar
H,H
H,H
3
ar 13
(
−
=
1/2
=
3
max
3
H,H
+
760.5 mV (vs Fc/Fc ).
[Cu (B12)](ClO
(
3
II
7
(
)
4
2
(C24
H
31Cl
2
CuN O13, M = 731.98 g/mol). The
5 W
+
ligand B12 (46.9 mg, 0.1 mmol, 1.0 equiv) was dissolved in 2.0 mL of
acetonitrile, and copper(II) perchlorate hexahydrate (37.1 mg, 0.1
mmol, 1.0 equiv) dissolved in further 2.0 mL of acetonitrile was added
to the solution. This blue solution was stirred at ambient temperature
overnight and afterward subjected to an ether diffusion. The product
was obtained as blue crystals in a yield of 69.4% (50.8 mg, 69.4 μmol).
HR-ESI (pos): [B12 + Cu + ClO
40. Elemental analysis: [B12 + Cu(ClO
9.57; obsd C, 39.35; H, 4.48; N, 9.52. UV (CH
(λmax), 983. CV (CH CN, rt): E1/2 = −807.0 mV (vs Fc/Fc ).
) (C26 32ClCuN = 673.56 g/mol). The
Cu complex [Cu (B13)](ClO ) (23.0 mg, 30.8 μmol) was dissolved
[
2
2
5
26
4
5
W
2
9
6
0
II
− +
] calcd 631.110 63, obsd 631.109
] calcd C, 39.38; H, 4.27; N,
CN, rt), λ [nm]: 627
4
)
4 2
3
+
3
II
[Cu (B13-H)](ClO
H
O10, M
5 W
4
II
II
4
2
1
in 1.0 mL of acetonitrile, and 0.1 mL of DIPEA was added to the blue
solution. Immediately, a purple precipitate formed. The suspension
3
4
3
3
H,H
8
140
dx.doi.org/10.1021/ic4008685 | Inorg. Chem. 2013, 52, 8131−8143