M. Gꢀmez-Gallego, M. A. Sierra et al.
121.8, 115.5 (ArC), 113.0 (d, J=33.9 Hz, Cb CꢁC), 81.8 (CH-O), 64.2
(JPtꢀP =2279.1 Hz); IR (film): n˜ = 3055, 2923, 2853, 2114 (CꢁC), 1755
(CH N), 41.2 (CH2 N), 28.6 (d, J=154.6 Hz, CH2 P), 28.4 ppm (CH2);
31P NMR (CHCl3, 121.4 MHz): d=42.6 ppm (JPtꢀP =2367.5 Hz); 31P NMR
[D6]acetone, 121.4 MHz): d=43.3 ppm (JPtꢀP =2344.8 Hz); IR (film): n˜ =
(C=O), 1597, 1493, 1235 (C O), 1105, 822, 751 cmꢀ1; FABMS: 2316.4
ꢀ
ꢀ
ꢀ
ꢀ
[M+H]+; m.p. 2458C (decomp); C126H106N4O8P4Pt2: calcd: C 65.34, H
4.53, N 2.42; found: C 65.43, H 4.60, N 2.30.
ꢀ
3054, 2922, 2110 (CꢁC), 1755 (C=O), 1597, 1493, 1234 (C O), 1104, 825,
General procedure for the synthesis of AgOTf complexes: To a solution
of the corresponding macrocycle in CDCl3 and under argon, AgOTf was
added in one portion. The ratios macrocycle/AgOTf used were 1:1 for
the monometallic macrocycles 21 and 22 and 1:2 for the bimetallic mac-
rocycles 23 and 24. The mixture was stirred for 3 h in the dark (a brown
precipitate was formed). The products were obtained by centrifugation
(3000 rpm, 30 min–1 h), followed by washing with CDCl3 and drying. The
AgOTf complexes were light-sensitive products.
750 cmꢀ1; m.p. 2358C; FABMS: 1158.5 [M+H]+; C63H53N2O4P2Pt: calcd:
C 65.34, H 4.53, N 2.42; found: C 65.39, H 4.65, N 2.35.
Compound 22: Following the general procedure, bis-b-lactam 12 (50 mg,
0.09 mmol), cis-[PtACHTUNGTRENNUNG(dppe)CAHTUNGTRNE(NUGN OTf)2] (78 mg, 0.09 mmol), and NaOAc
(47 mg, 0.35 mmol) were combined. After 12 h at room temperature and
further purification, 22 (62 mg, 61%) was obtained as a pale yellow solid.
1H NMR (CDCl3, 300 MHz): d=8.03–7.93 (m, 8H, ArH), 7.43 (m, 12H,
ArH), 7.33 (d, J=8.1 Hz, 4H, ArH), 7.13–7.05 (m, 8H, ArH), 6.85 (t, J=
7.3 Hz, 2H, ArH), 6.74 (d, J=7.8 Hz, 4H, ArH), 5.33 (d, J=4.4 Hz, 2H,
AgOTf complex 25: Complex 21 (20 mg, 17 mmol) and AgOTf (4.5 mg,
17 mmol) in CDCl3 (5 mL) were mixed together. After 3 h, silver triflate
complex 25 (20 mg, 82%) was obtained as a light brown solid. 1H NMR
([D6]acetone, 300 MHz): d=8.01–6.95 (m, 34H, ArH), 6.94–6.76 (m, 4H,
ꢀ
ꢀ
CH-O), 4.73 (d, J=4.4 Hz, 2H, CH N), 3.42–3.32 (m, 2H, CH2 N),
ꢀ
ꢀ
2.89–2.79 (m, 2H, CH2 N), 2.51–2.31 (m, 4H, CH2 P), 2.03–1.91 ppm
(m, 2H, CH2); 13C NMR (CDCl3, 75.5 MHz): d=165.8 (C=O), 157.0,
133.7–133.1 (m, dppe), 132.0, 131.3, 131.1, 129.9 (dd, J1 =54.7 Hz, J2 =
21.3 Hz, Ca CꢁC), 129.6, 129.1, 129.0–128.6 (m, dppe), 127.7, 121.8,
ꢀ
ꢀ
ArH), 5.60–5.53 (brs, 2H, CH O), 5.31–5.22 (brs, 2H, CH N), 3.64–3.43
ꢀ
ꢀ
ꢀ
(m, 2H, CH2 N), 3.22–3.02 (m, 2H, CH2 N), 2.92–2.64 (m, 4H, CH2 P),
1.69–1.48 ppm (m, 2H, CH2); 13C NMR ([D6]acetone, 176.0 MHz CDCl3):
d=165.3 (C=O), 157.0, 134.0–131.5 (m, dppe + ArC), 129.5, 128.9, 124.9,
ꢀ
ꢀ
115.6 (ArC), 113.1 (d, J=33.9 Hz, Cb CꢁC), 82.0 (CH O), 63.9 (CH
N), 40.0 (CH2 N), 29.7 (CH2 P), 27.4 ppm (CH2); 31P NMR (CHCl3,
ꢀ
ꢀ
ꢀ
ꢀ
120.5, 115.0 (ArC), 81.9 (CH-O), 63.3 (CH N), 40.4 (CH2 N), 30.7–28.0
(m, CH2 P), 26.9 ppm (CH2); 31P NMR ([D6]acetone, 121.4 MHz): d=
121.4 MHz): d=42.6 ppm (JPtꢀP =2359.3 Hz); IR (film): n˜ =2923, 2853,
ꢀ
ꢀ1
42.9 ppm (s, JPtꢀP =2621.9 Hz); 19F NMR ([D6]acetone, 282 MHz): d=
ꢀ78.9 ppm; IR (film): n˜ =3057, 2923, 2087 (CꢁC), 1756 (C=O), 1596,
ꢀ
2110 (CꢁC), 1759 (C=O), 1598, 1493, 1234 (C O), 1105, 840, 754 cm
;
m.p. 2438C (decomp); FABMS: 1158.8 [M+H]+; C63H53N2O4P2Pt: calcd:
1493, 1277, 1259, 1233 (C O), 1159, 1105, 1030, 825, 753 cmꢀ1; FABMS:
C 65.34, H 4.53, N 2.42; found: C 65.61, H 4.40, N 2.38.
ꢀ
1264.9 [MꢀOTf].+
General procedure for the synthesis of Pt–C complexes 23 and 24: To a
stirred solution of the bis-b-lactams 11 and 12 and cis-[PtACTHNUTRGNEUNG
(dppe)Cl2][29] in
AgOTf complex 26: Complex 22 (15 mg, 12 mmol) and AgOTf (3.3 mg,
12 mmol) were added together in CDCl3 (4 mL). After 3 h, AgOTf com-
plex 26 (12 mg, 65%) was obtained as a light brown solid. 1H NMR
([D6]acetone, 300 MHz): d=7.94–7.81 (m, 4H, ArH), 7.74–7.58 (m, 12H,
ArH), 7.32–7.02 (m, 16H, ArH), 6.94–6.84 (m, 6H, ArH), 5.57 (d, J=
CH2Cl2/Et3N (9:1; 100 mL), under an argon atmosphere, CuI (10%) was
added in a single portion. The reaction mixture was stirred at room tem-
perature for 12 h, quenched by addition of water (20 mL) and extracted.
The organic layer was dried over MgSO4, the solvent was removed under
reduced pressure, and the products were purified by chromatography on
silica gel (CH2Cl2/AcOEt/MeOH 6:3:1).
ꢀ
ꢀ
ꢀ
4.3 Hz, 2H, CH O), 5.23 (brs, 2H, CH N), 3.64–3.55 (m, 2H, CH2 N),
ꢀ
ꢀ
2.97–2.68 (m, 6H, CH2
N + CH2 P), 1.63–1.55 ppm (m, 2H, CH2);
13C NMR ([D6]acetone, 176.0 MHz): d=165.2 (C=O), 157.0, 133.9–133.6
Compounds 23a,b: Following the general procedure, bis-b-lactam 11
(m, dppe), 132.9–132.5 (m, dppe), 131.7, 130.4–130.2 (m, dppe), 129.5,
(40 mg, 0.07 mmol), cis-[PtACTHNUTRGNE(UGN dppe)Cl2] (44 mg, 0.07 mmol), and CuI
ꢀ
ꢀ
129.4–129.3 (m, dppe), 122.2, 115.3, (ArC), 82.6 (CH O), 63.4 (CH N),
(1.3 mg, 0.01 mmol) were added together. After 12 h at room tempera-
ture and further purification, a 1:1 syn/anti diastereomeric mixture of
doubly assembled compounds 23a and 23b (55 mg; 68%) was obtained
as a pale yellow solid. 1H NMR (CDCl3, 300 MHz): d=7.96–7.79 (m,
16H, ArH), 7.47–7.29 (m, 24H, ArH), 7.18–7.10 (m, 8H, ArH), 7.06–6.96
(m, 16H, ArH), 6.86–6.78 (m, 4H, ArH), 6.68–6.63 (m, 8H, ArH), 5.27–
41.7 (CH2 N), 29.6.7–28.5 (m, CH2 P), 29.4 ppm (CH2); 31P NMR
([D6]acetone, 121.4 MHz): d=42.4 ppm (JPtꢀP =2577.9 Hz); 19F NMR
([D6]acetone, 282 MHz): d=ꢀ79.1 ppm; IR (film): n˜ =3061, 2960, 2919,
ꢀ
ꢀ
ꢀ
2056 (CꢁC), 1761 (C=O), 1594, 1491, 1261, 1233 (C O), 1159, 1102,
1030, 801, 754 cmꢀ1; ESI-MS: 1264.23 [MꢀOTf].+
ꢀ
ꢀ
5.25 (m, 4H, CH O), 4.58–4.56 (m, 4H, CH N), 3.37–3.30 (m, 4H,
AgOTf complexes 27: The mixture of diastereoisomers 23a,b (20 mg, 8
mmol) and AgOTf (4.5 mg, 17 mmol) were mixed together in CDCl3
(5 mL). After 3 h, AgOTf complexes 27 (18 mg, 75%; mixture of diaste-
reoisomers) were obtained as a light brown solid. 1H NMR ([D6]acetone,
300 MHz): d=8.07–7.73 (m, 16H, ArH), 7.72–7.30 (m, 24H, ArH), 7.23–
7.02 (m, 16H, ArH), 6.97–6.60 (m, 20H, ArH), 5.56–5.52 (m, 4H, CH-
O), 5.13–5.08 (m, 4H, CH-N), 3.44–3.26 (m, 4H, CH2-N), 3.15–2.83 (m,
ꢀ
ꢀ
ꢀ
CH2 N), 3.00–2.91 (m, 4H, CH2 N), 2.51–2.29 (m, 8H, CH2 P), 1.59–
1.50 ppm (m, 4H, CH2); 13C NMR (CDCl3, 75.5 MHz): d=166.0 (C=O),
156.6, 156.5 133.7–133.1 (m, dppe), 132.0, 131.5–131.1 (m), 129.9–129.7
(m, Ca CꢁC), 129.3, 129.2, 128.8–128.5 (m, dppe), 127.8, 121.8, 115.5,
ꢀ
ꢀ
115.4 (ArC), 111.6–111.1 (m, Cb CꢁC), 81.6, (CH O), 62.0, 61.9 (CH
N), 37.6 (CH2 N), 30.5–27.8 (m, CH2 P), 24.5, 24.4 ppm (CH2); 31P NMR
ꢀ
ꢀ
+
CH2-P), 1.41–1.26 ppm (m, 4H, CH2); 13C NMR
(CHCl3, 121.4 MHz): d=42.4, 42.3 ppm (JPtꢀP =2288.8 Hz); IR (KBr):
12H, CH2-N
ꢀ
n˜ = 3056, 2923, 2853, 2114 (CꢁC), 1760 (C=O), 1597, 1493, 1235 (C O),
([D6]acetone, 75.5 MHz): d=165.5, 165.4 (C=O), 157.8, 156.7, 135.5,
135.4, 133.9–133.8 (m, dppe), 133.5–133.4 (m, dppe), 132.8–132.7 (m,
dppe), 132.4, 132.1, 132.09, 132.03, 131.3, 131.2, 129.4–129.1 (m, dppe),
128.8, 128.5, 122.4, 122.3, 121.8, 121.7, 115.1, 114.9 (ArC), 81.9, 81.6
1105, 828, 750 cmꢀ1; FABMS: 2315.7 [M+H]+; m.p. 2408C (decomp);
C126H106N4O8P4Pt2: calcd: C 65.34, H 4.53, N 2.42; found: C 65.49, H 4.34,
N 2.31.
ꢀ
ꢀ
ꢀ
ꢀ
(CH O), 62.8, 62.7 (CH N), 40.1, 40.0 (CH2 N), 29.8–28.8 (m, CH2 P),
28.0, 27.8 ppm (CH2); 31P NMR ([D6]acetone, 121.4 MHz): d=44.0
(JPtꢀP =2516.1 Hz), 43.9 ppm (JPtꢀP =2510.8 Hz); 19F NMR ([D6]acetone,
282 MHz): d=ꢀ78.9 ppm; IR (film): n˜ =3064, 2926, 2854, 1759 (C=O),
Compounds 24a,b: Following the general procedure, of bis-b-lactam 12
(70 mg, 0.12 mmol), cis-[PtACTHNUTRGNE(UGN dppe)Cl2] (78 mg, 0.12 mmol), and CuI
(2.6 mg, 0.02 mmol) were added together. After 12 h at room tempera-
ture and further purification, a 1:1 syn/anti diastereomeric mixture of
doubly assembled compounds 24a and 24b (27 mg, (23%) was obtained
as a pale yellow solid. 1H NMR (CDCl3, 300 MHz): d=7.99–7.79 (m,
16H, ArH), 7.45–7.31 (m, 24H, ArH), 7.15–6.97 (m, 24H, ArH), 6.82–
1597, 1494, 1284, 1237 (C O), 1168, 1108, 1031, 826, 756 cmꢀ1; ESI-MS:
ꢀ
2680.40 [MꢀOTf],+ 2421.57 [MꢀAgꢀ2OTf],+ 1264.74 [Mꢀ2OTf].2+
AgOTf complexes 28: The mixture of diastereoisomers 24a,b (15 mg, 6
mmol) and AgOTf (3.3 mg, 12 mmol) were added together in CDCl3
(4 mL). After 3 h, AgOTf complexes 28 (11 mg, 60%; mixture of diaste-
reoisomers) were obtained as a light-brown solid. 1H NMR ([D6]acetone,
300 MHz): d=8.10–7.86 (m, 16H, ArH), 7.75–7.29 (m, 24H, ArH), 7.20–
ꢀ
6.72 (m, 4H, ArH), 6.70–6.62 (m, 8H, ArH), 5.29–5.29 (m, 4H, CH O),
ꢀ
ꢀ
4.65–4.62 (m, 4H, CH N), 3.40–3.23 (m, 4H, CH2 N), 3.03–2.89 (m, 4H,
ꢀ
ꢀ
CH2 N), 2.55–2.28 (m, 8H, CH2 P), 2.09–1.95 (m, 2H, CH2), 1.75–
1.60 ppm (m, 2H, CH2); 13C NMR (CDCl3, 75.5 MHz): d=166.0 (C=O),
156.7, 156.6 133.7–133.1 (m, dppe), 131.2, 131.1, 129.9, 129.7, 129.4, 129.3,
129.2, 129.1, 128.8–128.4 (m, dppe), 127.8, 127.7, 121.8, 115.6, 115.5 (ArC
ꢀ
6.89 (m, 24H, ArH), 6.77–6.64 (m, 12H, ArH), 5.51–5.43 (m, 4H, CH
ꢀ
ꢀ
O), 5.02–4.93 (m, 4H, CH N), 3.54–2.75 (m, 16H, CH2 N), 1.44–
1.20 ppm (m, 4H, CH2); 13C NMR ([D6]acetone, 176.0 MHz): d=165.1,
164.9 (C=O), 156.9, 135.8, 135.5, 134.1–133.9 (m, dppe), 133.6–133.4 (m,
ꢀ
ꢀ
ꢀ
+ CꢁC), 81.8, 81.7 (CH O), 62.5 (CH N), 38.3 (CH2 N), 29.8–28.3 (m,
CH2 P), 26.1 ppm (CH2); 31P NMR (CHCl3, 121.4 MHz): d=42.3 ppm
ꢀ
6950
ꢃ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 6940 – 6952