Full Paper
3
3
1
3
1
1
2
(
dd, J =11.7 Hz, J =17.8 Hz, 1H; 3 -H), 6.35 (d, J =17.8 Hz,
3.02 (s, 3H; 2 -H), 2.88 (s, 3H; 7 -H), 2.54–2.42 (m, 1H; 17 -H), 2.54–
cis
2
trans
3
trans
2
1
2
1
4
3
H; 3
-H), 6.17 (d, J =11.7 Hz, 1H; 3 cis-H), 4.90 (m, 1H; 17-H),
2.42 (m, 1H; 17 -H), 2.38–2.30 (m, 1H; 17 -H), 2.18–2.09 (m, 1H;
trans
cis
2
3
.46–4.41 (m, 4H; 2’, 3’, 4’, 5’), 4.38 (m, 1H; 18-H), 4.05 (s, 5H; 1’’),
.73 (q, J=7.6 Hz, 2H; 8 -H), 3.66 (s, 3H; 12 -H), 3.54 (s, 3H; 17 -
H), 3.39 (s, 3H; 2 -H), 3.22 (s, 3H; 7 -H), 2.53 (m, 1H; 17 -H), 2.31
m, 1H; 17 -H), 2.23 (m, 1H; 17 -H), 1.93 (m, 1H; 17 -H), 1.75 (d,
17 -H), 1.94 (s, 15H; 2’’-H), 1.94 (brs, 1H; NH), 1.67 (d, J=7.2 Hz,
1 3 2 13
3
1
1
5
3H; 18 -H), 1.53 ppm (t, J=7.7 Hz, 3H; 8 -H); C NMR (126 MHz,
1
1
2
3
CD Cl ): d=173.5 (17 ), 172.3 (19), 162.8 (16), 151.0 (6), 148.8 (9),
148.3 (14), 144.9 (1), 142.5 (8), 140.7 (11), 139.8 (13), 136.2 (3), 136.0
2
2
1
2
1
(
3
1
3
2
1
1
J=7.3 Hz, 3H; 18 -H), 1.72 (t, J=7.6 Hz, 3H; 8 -H), À0.22 (brs,
(13 ), 135.4 (4), 133.8 (7), 129.6 (2), 129.04 (3 ), 128.95 (12), 125.9
1
3
2
2
1
1
1
1
1
(
(
1
H; NH), À0.29 ppm (brs, 1H; NH); C NMR (126 MHz, CD Cl ): d=
(13 ), 121.4 (3 ), 113.5 (15), 106.8 (10), 101.5 (5), 92.3 (20), 85.5 (1’’),
2
2
1
1
3
5
96.4 (13 ), 191.2 (15 ), 173.3 (17 ), 173.1 (19), 172.2 (16), 154.8 (6),
49.5 (9), 145.4 (8), 142.4 (1), 137.7 (14), 137.6 (11), 136.59 (7),
83.9 (1’), 73.5 (3’ and 4’), 71.6 and 71.3 (4’ and 5’), 51.5 (17 ), 50.8
(17), 48.7 (18), 32.0 (17 ), 30.9 (17 ), 22.6 (18 ), 19.0 (8 ), 17.1 (8 ),
13.4 (12 ), 11.43 (2’’), 11.43 (2 ), 10.4 ppm (7 ); HRMS (ESI-TOF): m/z
calcd for C H N O Ru [M+H] : 833.3363; found: 833.3343 (D=
1
2
1
1
2
1
1
1
1
36.56 (3), 135.5 (4), 130.9 (2), 130.23 (12), 130.20 (13), 128.8 (3 ),
22.6 (3 ), 106.8 (10), 105.8 (15), 102.7 (5), 94.4 (20), 84.3 (1’), 72.1
3’ and 4’), 71.1/70.8 (2’ and 5’), 69.6 (1’’), 52.7 (17), 51.4 (17 ), 48.7
18), 32.4 (17 ), 31.4 (17 ), 23.5 (18 ), 19.5 (8 ), 17.4 (8 ), 12.3 (12 ),
1.9 (2 ), 10.9 ppm (7 ); UV/Vis (THF): l
06 (5), 411 nm (100); HRMS (ESI-TOF): m/z calcd for C H FeN O
4
M+H] : 749.2785; found: 749.2785 (D=0.03 ppm).
2
+
49
55
4
2
5
2.46 ppm).
1
2
1
1
2
1
1
1
(%)=697 (34), 545 (7),
max
5
5
[
Pentamethylruthenocenylchlorins (R)-14, (S)-14 and 15: [Ru(h -
4
4
45
4
+
4
C Me )(h -C H )Cl] (16 mg, 0.042 mmol) was added to a stirred
5
5
8
12
mixture of fulvene 12 (25 mg, 0.042 mmol) and TEA (5 mL,
.042 mmol) in THF (3 mL). The reaction mixture was stirred at RT
0
Fulvenylchlorin 12: Pyrrolidine (94 mL, 1.16 mmol, 2 equiv) was
added dropwise to a stirred mixture of 1 (317 mg, 0.58 mmol,
under argon for 20 min until product 13 had formed and there
was no starting material left. Then the reaction mixture was stirred
in air for 10 min until 13 had fully oxidised to give compounds (R/
S)-14 and 15. These products were separated by column chroma-
tography on SiO2 (10:1!1:1 hexane/EtOAc) eluting first green
compounds (R)- and (S)-14 separately and finally red compound
1
3
equiv) and freshly distilled cyclopentadiene (143 mL, 1.73 mmol,
equiv) in THF/MeOH (1:1; 16 mL). The reaction mixture was
stirred at 508C under argon for 4 days. Solvents were evaporated
and the crude product was purified by column chromatography
on SiO2 (5:1!3:1; hexane/EtOAc, gradient) to afford yellowish
1
5. (R)-14: Yield: ꢀ8 mg, 0.0094 mmol, 22%; R =0.7 (3:1 hexane/
f
brown product 12 (279 mg, 81%). R =0.8 (1:1 hexane/EtOAc);
f
1
EtOAc); H NMR (500 MHz, CDCl ): d=9.80 (s, 1H; 5-H), 9.46 (s, 1H;
1
3
H NMR (300 MHz, CD Cl ): d=9.59 (s, 1H; 5-H), 9.53 (s, 1H; 10-H),
.82 (s, 1H; 20-H), 8.13 (dd, J =11.7 Hz, J =17.8 Hz, 1H; 3 -H),
cis trans
.50 (m, 1H; 2’-H), 7.15 (m, 1H; 5’-H), 6.81 (m, 1H; 3’-H), 6.78 (m,
H; 4’-H), 6.34 (dd, J =1.5 Hz, J =17.8 Hz, 1H; 3 trans-H), 6.17
2
2
3
3
1
3
1
4
3
0-H), 8.79 (s, 1H; 20-H), 8.12 (dd, J =11.7 Hz, J =17.8 Hz, 1H;
cis trans
3
3
1
8
7
1
1
3
2
3
-H), 6.28 (d, J =17.8 Hz, 1H; 3
-H), 6.14 (d, J =11.7 Hz,
cis
trans
trans
2
1
H; 3 -H), 5.42 (s, 1H; 13 -H), 4.99 (m, 1H; 17-H), 4.91 (s, 1H; 2’),
2
3
2
cis
gem
trans
2
.72 (s, 1H; 5’), 4.53 (m, 1H; 18-H), 4.20 (s, 1H; 3’), 4.16 (s, 1H; 4’),
.74 (q, J=7.6 Hz, 2H; 8 -H), 3.63 (s, 3H; 17 -H), 3.59 (s, 3H; 12 -
2
3
2
(
dd, J =1.5 Hz, J =11.7 Hz, 1H; 3 -H), 5.98 (d, J =20.0 Hz,
gem
2
cis
2
cis
gem
3
1
5
1
2’
1
4
3
H; 13 -H), 5.84 (d, J =20.0 Hz, 1H; 13 -H) 4.61 (m, 1H; 18-H),
.47 (m, 1H; 17-H), 3.72 (m, 2H; 8 -H), 3.71 (s, 3H; 12 -H) 3.60 (s,
H; 17 -H), 3.49 (s, 3H; 2 -H), 3.29 (s, 3H; 7 -H), 2.77 (m, 1H; 17 -
gem
1
1
1
H), 3.45 (s, 3H; 2 -H), 3.31 (s, 3H; 7 -H), 2.88 (m, 1H; 17 -H), 2.76
1
1
2
2
1
(
m, 1H; 17 -H), 2.45 (m, 1H; 17 -H), 2.30 (m, 1H; 17 -H), 1.84 (s,
5
1
1
1
3
1
3
2
1
5H; 2’’), 1.76 (d, J=7.2 Hz, 3H; 18 -H), 1.71 (t, J=7.6 Hz, 3H; 8 -
13
2
1
2
H), 2.63 (m, 1H; 17 -H), 2.31 (m, 1H; 17 -H), 2.31 (m, 1H; 17 -H),
H), 0.24 (brs, 1H; NH), À1.70 ppm (brs, 1H; NH); C NMR
3
1
3
2
1
(
.86 (d, J=7.3 Hz, 3H; 18 -H), 1.72 (t, J=7.7 Hz, 3H; 8 -H), À0.42
2
3
(
126 MHz, CDCl ): d=203.3 (13 ), 173.8 (17 ), 169.0 (19), 168.7 (16),
13
3
brs, 1H; NH), À2.43 ppm (brs, 1H; NH); C NMR (126 MHz,
1
52.5 (9), 151.6 (14), 148.9 (6), 142.3 (8), 140.1 (11), 138.8 (1), 137.5
3
CD Cl ): d=173.5 (17 ), 169.3 (19), 161. 5 (16), 152.9 (6), 150.8 (9),
2
2
1
(
7),136.6 (13), 135.2 (3), 130.8 (4), 129.8 (3 ), 128.3 (12), 127.4 (2),
1
1
47.2 (14), 146.2 (11), 144.3 (8), 140.0 (13), 139.8 (1), 138.0 (1’),
36.4 (7), 136.0 (12), 134.8 (3), 134.3 (4), 130.6 (3’), 130.5 (2), 130.3
2
1
21.7 (3 ), 105.7 (15), 104.6 (5), 101.1 (10), 95.7 (20), 89.2 (1’), 85.3
5
(
(
1’’), 73.0 (4’), 72.6 (2’), 72.4 (3’), 71.4 (5’), 53.6 (17), 51.5 (17 ), 48.0
1 2 1 1 1 2
1
1
2
(
4’), 129.6 (3 ), 126.1 (13 ), 122.9 (2’), 122.3 (5’), 121.7 (3 ), 108.0
13 ), 47.7 (18), 32.2 (17 ), 30.9 (17 ), 24.2 (18 ), 19.5 (8 ), 17.6 (8 ),
5
(
15), 101.0 (10), 97.4 (5), 93.5 (20), 52.6 (17), 51.5 (17 ), 49.7 (18),
1
1
1
1
6
3.0 (12 ), 12.1 (2 ), 11.9 (2’’), 11.3 ppm (7 ); UV/Vis (THF): l (%)=
2
2
1
1
1
2
max
4
4.2 (13 ), 30.9 (17 ), 29.7 (17 ), 23.4 (18 ), 19.5 (8 ), 17.4 (8 ), 15.0
66 (32), 534 (6), 499 (7), 400 nm (100); HRMS (ESI-TOF): m/z calcd
1
1
1
(
12 ), 12.1 (2 ), 11.1 ppm (7 ); HRMS (ESI-TOF): m/z calcd for
+
for C H N O Ru [M+H] : 849.3312; found: 849.3295 (D=
+
49 55
4
3
C H N O [M+H] : 597.3224; found: 597.3245 (D=3.50 ppm).
39
41
4
2
2
.04 ppm). (S)-14: Yield: ꢀ8 mg, 0.0094 mmol, 22%; R =0.6 (3:1
f
1
hexane/EtOAc); H NMR (500 MHz, CDCl ): d=9.82 (s, 1H; 5-H),
9.52 (s, 1H; 10-H), 8.82 (s, 1H; 20-H), 8.11 (dd, J =11.7 Hz, J
3
5
4
3
3
Pentamethylruthenocenylchlorin 13: [Ru(h -C Me )(h -C H )Cl]
=
trans
5
5
8
12
cis
1
3
2
(
(
15 mg, 0.039 mmol) was added to a stirred mixture of fulvene 12
23 mg, 0.039 mmol) and TEA (5 mL, 0.039 mmol) in THF (3 mL). Re-
17.8 Hz, 1H; 3 -H), 6.28 (d, Jtrans =17.8 Hz, 1H; 3 trans-H), 6.15 (d,
3
2
cis
1
Jcis =11.7 Hz, 1H; 3 -H), 5.63 (s, 1H; 13 -H), 5.07 (s, 1H; 2’), 5.03
action mixture was stirred at RT under argon for 20 min. The reac-
tion mixture was submitted to column chromatography on SiO2.
Purification by flash chromatography (3:1 hexane/EtOAc) was per-
formed under an argon flow and the eluent was bubbled with
argon before use to prevent oxidation of product 13. The product
fraction was quickly evaporated to dryness and dried under
vacuum to give brown product 13 (29 mg, 91%). The air-sensitive
(m, 1H; 17-H), 4.83 (s, 1H; 5’), 4.51 (m, 1H; 18-H), 4.24 (s, 1H; 3’),
4.20 (s, 1H; 4’), 3.76 (q, J=7.5 Hz, 2H; 8 -H), 3.65 (s, 3H; 12 -H),
3
1
1
5
1
1
3.52 (s, 3H; 17 -H), 3.46 (s, 3H; 2 -H), 3.33 (s, 3H; 7 -H), 2.63 (m,
1
2
1
1H; 17 -H), 2.63 (m, 1H; 17 -H), 2.19 (m, 1H; 17 -H), 2.19 (m, 1H;
2
3
1
3
2
17 -H), 1.84 (d, J=6.6 Hz, 3H; 18 -H), 1.75 (t, J=7.5 Hz, 3H; 8 -H)
1.46 (s, 15H; 2’’), 0.26 (brs, 1H; NH), 1.68 ppm (brs, 1H; NH);
13
2
3
C NMR (126 MHz, CDCl ): d=202.7 (13 ), 173.8 (17 ), 168.9 (19),
3
1
product was characterised immediately. H NMR (500 MHz, CD Cl ):
168.8 (16), 152.5 (9), 152.1 (14), 149.0 (6), 142.4 (8), 140.1 (11), 138.8
2
2
3
1
d=8.56 (s, 1H; 5-H), 8.43 (s, 1H; 10-H), 7.65 (dd, J =11.7 Hz,
(1), 137.6 (7), 135.6 (13), 135.3 (3), 130.8 (4), 129.7 (3 ), 128.6 (12),
cis
3
1
2
2
Jtrans =17.8 Hz, 1H; 3 -H), 7.64 (s, 1H; 20-H), 6.50 (s, 1H; 13 -H),
127.4 (2), 121.8 (3 ), 104.2 (15), 103.9 (5), 101.1 (10), 95.8 (20), 88.3
3
2
3
2
6
.06 (d, J =17.8 Hz, 1H; 3
-H), 5.96 (d, J =11.7 Hz, 1H; 3 cis-
(1’), 85.0 (1’’), 72.9 (3’), 72.64 (4’), 72.58 (2’), 71.6 (5’), 53.5 (17), 51.4
trans
trans
cis
5
1
2
1
1
1
H), 4.86 and 4.82 (each s, 1H; 2’- and 5’-H), 4.43 (s, 2H; 3’- and 4’-
(17 ), 47.9 (13 ), 47.8 (18), 31.7 (17 ), 30.4 (17 ), 24.4 (18 ), 19.6 (8 ),
2
1
1
1
H), 3.91 (m, 1H; 18-H), 3.86 (m, 1H; 17-H), 3.70 (brs, 1H; NH), 3.66
17.6 (8 ), 13.4 (12 ), 12.1 (2 ), 11.6 (2’’), 11.3 ppm (7 ); UV/Vis (THF):
lmax (%)=666 (32), 533 (5), 499 (6), 400 nm (100); HRMS (ESI-TOF):
5
3
1
1
(
s, 3H; 17 -H), 3.33 (q, J=7.6 Hz, 2H; 8 -H), 3.09 (s, 3H; 12 -H),
Chem. Eur. J. 2015, 21, 12755 – 12768
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim