D. Harmsen, G. Erker, R. Fröhlich, G. Kehr
6.25 (2 ϫ s, 2 ϫ 5 H, Cp-H and CpЈ-H), 5.19 (br., 1 H, 2-H), 3.86 IR (KBr): ν˜ ϭ 3357 (br., NH), 3055 (w), 2985 (w), 1743 (m, COO),
FULL PAPER
(m, 1 H, 3-H), 3.82 (m, 1 H, 6-H), 3.78 (s, 3 H, 10-OCH3), 3.57
1660 (s, CON), 1616 (vs, CON), 1521 (m), 1481 (m), 1454 (s),
1237 (m), 1065 (m), 1018 (m), 825 (s), 734 (s), 705 (vs), 613 (m)
(ABX, 2J ϭ 17.3 Hz, 2 H, 9-H and 9-HЈ), 1.44 [s, 9 H, 1-
OC(CH3)3], 1.29 (d, 3J ϭ 7.2 Hz, 3 H, 3-CH3), 1.15 (s, 3 H, cmϪ1. H NMR: δ ϭ 7.45 (br. d, J ϭ 8.8 Hz, 1 H, 8-H), 7.37 [m,
1
3
3
TiϪCH3), 1.13 (d, J ϭ 7.3 Hz, 3 H, 6-CH3) ppm. 13C NMR: δ ϭ 5 H, 1-OCH2(C6H5)], 6.09 and 6.01 (2 ϫ s, 2 ϫ 5 H, Cp-H and
183.6 (C-7), 173.3 (C-4), 167.2 (C-10), 157.9 (C-1), 116.9 and 116.8 CpЈ-H), 5.39 (br. d, 3J ϭ 6.3 Hz, 1 H, 2-H), 5.11 [AB, 2J ϭ 12.3 Hz,
3
(C-Cp and C-CpЈ), 82.4 [1-OC(CH3)3], 53.3 (10-OCH3), 52.3 (C-
3), 51.4 (TiϪCH3), 49.7 (C-6), 41.9 (C-9), 28.1 [1-OC(CH3)3], 16.7 H, 9-H), 3.94 (m, 1 H, 3-H), 3.79 (s, 3 H, 10-OCH3), 1.51 (d, J ϭ
(3-CH3), 16.3 (6-CH3) ppm.
2 H, 1-OCH2(C6H5)], 4.91 (q, J ϭ 7.0 Hz, 1 H, 6-H), 4.30 (m, 1
3
3
7.0 Hz, 3 H, 6-CH3), 1.42 (d, J ϭ 7.3 Hz, 3 H, 9-CH3), 1.31 (d,
3J ϭ 7.0 Hz, 3 H, 3-CH3) ppm. 13C NMR: δ ϭ 178.0 (C-7), 173.9
(C-4), 171.4 (C-10), 156.1 (C-1), 138.8Ϫ122.1 {1-OCH2(C6H5) and
[BPh4]Ϫ}, 118.4 and 118.2 (C-Cp and C-CpЈ), 67.3 [1-
OCH2(C6H5)], 58.9 (C-6), 53.3 (10-OCH3), 50.2 (C-9), 48.3 (C-3),
21.0 (6-CH3), 17.1 (9-CH3), 15.9 (3-CH3) ppm. C52H54BN3O6Ti
(875.7): calcd. C 71.32, H 6.22, N 4.80; found C 71.28, H 6.33,
N 4.73.
Products Boc-7(chelA)/Boc-7(chelB) ؍
1:2: Reaction of Boc-7(pept)
(151 mg, 4.56·10Ϫ4 mol) with 13 (266 mg, 4.56·10Ϫ4 mol) yielded
347 mg (92%) of the isomeric mixture Boc-7(chelA)/Boc-7(chelB) ϭ
1:2. M.p. (DSC): 68 °C (dec.). [α]D ϭ Ϫ33 (c ϭ 1.0, CH2Cl2). IR
(KBr): ν˜ ϭ 3315 (s, NH), 3281 (m, NH), 2980 (w), 1765 (w, COO),
1747 (m, COO), 1676 (s, CON), 1641 (vs, CON), 1518 (s), 1456 (w),
1261 (s), 1168 (m), 1099 (vs), 1022 (s), 802 (s), 742 (w), 706 (m)
cmϪ1. C48H54BN3O6Ti (827.7): calcd. C 69.66, H 6.58, N 5.08;
Boc-8(pept) (Boc-Ala-Ala-Ala-OMe):[36] Reaction of Boc-Ala-Ala-
OH (1.05 g, 4.03 mmol) with HCl·H-Ala-OMe (563 mg,
4.03 mmol), triethylamine (0.56 mL, 4.03 mmol), and IIDQ (1.22 g,
4.03 mmol) yielded 1.11 g (80%) of Boc-8(pept). M.p. (DSC): 185
°C. [α]D ϭ Ϫ48 (c ϭ 1.0, CH2Cl2). IR (KBr): ν˜ ϭ 3298 (s, NH),
3272 (s, NH), 2981 (m), 1744 (s, COO), 1709 (s, CON), 1692 (s,
CON), 1675 (s, CON), 1638 (vs, CON), 1550 (s), 1524 (s), 1456 (m),
1
found C 68.91, H 7.02, N 4.82. Boc-7(chelA): H NMR: δ ϭ 7.55
(br., 1 H, 5-H), 6.13 and 6.12 (2 ϫ s, 2 ϫ 5 H, Cp-H and CpЈ-H),
3
5.76 (ABX, 1 H, 8-H), 4.55 (q, J ϭ 6.9 Hz, 1 H, 3-H), 4.09 (m, 1
2
H, 6-H), 3.80 (ABX, J ϭ 18.2 Hz, 2 H, 9-H and 9-HЈ), 3.72 (s, 3
3
H, 10-OCH3), 1.54 (d, J ϭ 7.1 Hz, 3 H, 3-CH3), 1.53 [s, 9 H, 1-
OC(CH3)3], 1.32 (d, 3J ϭ 7.0 Hz, 3 H, 6-CH3) ppm. 13C NMR:
δ ϭ 178.2 (C-4), 170.5 (C-7), 169.9 (C-10), 152.6 (C-1), 118.4 and
118.1 (C-Cp and C-CpЈ), 84.2 [1-OC(CH3)3], 59.3 (C-3), 52.6 (10-
OCH3), 50.5 (C-6), 41.3 (C-9), 28.7 [1-OC(CH3)3], 18.8 (6-CH3),
18.4 (3-CH3) ppm. Boc-7(chelB): 1H NMR: δ ϭ 6.10 and 6.09 (2
ϫ s, 2 ϫ 5 H, Cp-H and CpЈ-H), 6.01 (ABX, 1 H, 8-H), 5.04 (br.
d, 3J ϭ 5.8 Hz, 1 H, 2-H), 4.79 (q, 3J ϭ 7.1 Hz, 1 H, 6-H), 3.89
(m, 1 H, 3-H), 3.74 (s, 3 H, 10-OCH3), 3.32 (ABX, 2 H, 9-H and
9-HЈ), 1.46 [s, 9 H, 1-OC(CH3)3], 1.35 (d, 3J ϭ 7.0 Hz, 3 H, 6-
CH3), 1.28 (d, 3J ϭ 7.1 Hz, 3 H, 3-CH3) ppm. 13C NMR: δ ϭ
178.5 (C-7), 174.6 (C-4), 168.4 (C-10), 155.5 (C-1), 118.4 and 118.0
(C-Cp and C-CpЈ), 80.6 [1-OC(CH3)3], 58.7 (C-6), 52.8 (10-OCH3),
47.9 (C-3), 42.5 (C-9), 28.1 [1-OC(CH3)3], 20.9 (6-CH3), 15.9 (3-
CH3) ppm.
1365 (w), 1252 (m), 1218 (m), 1170 (m), 1052 (w), 703 (br. w) cmϪ1
.
C15H27N3O6 (345.4): calcd. C 52.16, H 7.88, N 12.17; found C
52.84, H 7.87, N 12.07.
Reaction of Boc-8(pept) with 13: Boc-8(coord7): 1H NMR: δ ϭ 9.07
3
(br. d, 3J ϭ 8.2 Hz, 1 H, 8-H), 6.40 (br. d, J ϭ 5.0 Hz, 1 H, 5-H),
2 ϫ 6.29 (2 ϫ s, 2 ϫ 5 H, Cp-H and CpЈ-H), 5.12 (br. d, 3J ϭ
2.2 Hz, 1 H, 2-H), 3.90 (m, 1 H, 3-H), 3.88 (m, 1 H, 9-H), 3.80 (s,
3
3 H, 10-OCH3), 3.80 (m, 1 H, 6-H), 1.48 (d, J ϭ 7.3 Hz, 3 H, 9-
CH3), 1.45 [s, 9 H, 1-OC(CH3)3], 1.32 (d, 3J ϭ 7.3 Hz, 3 H, 3-CH3),
1.14 (s, 3 H, TiϪCH3), 1.32 (d, 3J ϭ 7.4 Hz, 3 H, 6-CH3) ppm. 13
C
NMR: δ ϭ 182.7 (C-7), 172.6 (C-4), 169.9 (C-10), 157.6 (C-1),
116.9 and 116.8 (C-Cp and C-CpЈ), 82.3 [1-OC(CH3)3], 53.3 (10-
OCH3), 52.2 (C-3), 51.7 (TiϪCH3), 49.9 (C-9), 49.8 (C-6), 27.9 [1-
OC(CH3)3], 16.9 (3-CH3), 16.8 (9-CH3), 16.4 (6-CH3) ppm.
Z-8(pept) (Z-Ala-Ala-Ala-OMe):[35] Reaction of Z-Ala-Ala-OH
(1.00 g, 3.40 mmol) with HCl·H-Ala-OMe (474 mg, 3.40 mmol),
triethylamine (0.47 mL, 3.40 mmol), and IIDQ (1.03 g, 3.40 mmol)
yielded 0.92 g (71%) of Z-8(pept). M.p. (DSC): 174 °C. [α]D ϭ Ϫ30
(c ϭ 1.0, CH2Cl2). IR (KBr): ν˜ ϭ 3303 (s, NH), 3275 (s, NH),
3068 (w), 2984 (w), 1739 (s, COO), 1689 (s, CON), 1640 (vs, CON),
1542 (s), 1455 (w), 1331 (w), 1257 (s), 1231 (m), 1158 (w), 1052 (m),
697 (m) cmϪ1. C18H25N3O6 (379.4): calcd. C 56.98, H 6.64, N
11.08; found C 57.00, H 6.80, N 10.92.
Products Boc-8(ChelA)/Boc-8(ChelB) ؍
3:2: Reaction of Boc-
8(pept) (117 mg, 3.39·10Ϫ4 mol) with 13 (198 mg, 3.39·10Ϫ4 mol)
yielded 251 mg (88%) of the isomeric mixture Boc-8(ChelA)/Boc-
8(ChelB) ϭ 3:2. M.p. (DSC): 68 °C (dec.). [α]D ϭ Ϫ20 (c ϭ 1.0,
CH2Cl2). IR (KBr): ν˜ ϭ 3301 (br., NH), 3054 (w), 2981 (m),
1743 (m, COO), 1695 (s, CON), 1653 (vs, CON), 1617 (vs, CON),
1522 (s), 1480 (s), 1451 (s), 1262 (m), 1157 (m), 1066 (m), 1018 (s),
820 (s), 733 (m), 704 (vs) cmϪ1. C49H56BN3O6Ti (841.7): calcd. C
69.92, H 6.71, N 4.99; found C 71.07, H 7.45, N 4.55. Boc-8(ChelA):
1H NMR: δ ϭ 7.39 (br., 1 H, 5-H), 6.10 and 6.07 (2 ϫ s, 2 ϫ 5 H,
Cp-H and CpЈ-H), 5.98 (br. d, 3J ϭ 7.2 Hz, 1 H, 8-H), 4.52 (q,
3J ϭ 6.9 Hz, 1 H, 3-H), 4.43 (m, 1 H, 9-H), 4.09 (m, 1 H, 6-H),
Reaction of Z-8(pept) with 13. Z-8(coord7): 1H NMR: δ ϭ 8.78 (br.
3
d, J ϭ 8.4 Hz, 1 H, 8-H), 7.38 [m, 5 H, 1-OCH2(C6H5)], 6.36 (br.
3
d, J ϭ 5.0 Hz, 1 H, 5-H), 2 ϫ 6.27 (2 ϫ s, 2 ϫ 5 H, Cp-H and
CpЈ-H), 5.44 (br. d, 1 H, 2-H), 5.11 [AB, 2J ϭ 12.0 Hz, 2 H, 1-
OCH2(C6H5)], 3.95 (m, 1 H, 3-H), 3.86 (m, 1 H, 9-H), 3.81 (s, 3
H, 10-OCH3), 3.80 (m, 1 H, 6-H), 1.45 (d, 3J ϭ 7.2 Hz, 3 H, 9-
3
3.72 (s, 3 H, 10-OCH3), 1.54 (d, J ϭ 7.3 Hz, 3 H, 3-CH3), 1.52 [s,
9 H, 1-OC(CH3)3], 1.35 (d, 3J ϭ 8.0 Hz, 3 H, 6-CH3), 1.35 (d, 3J ϭ
7.7 Hz, 3 H, 9-CH3) ppm. 13C NMR: δ ϭ 178.1 (C-4), 172.8 (C-
10), 169.7 (C-7), 152.7 (C-1), 118.4 and 118.1 (C-Cp and C-CpЈ),
84.2 [1-OC(CH3)3], 59.3 (C-3), 52.9 (10-OCH3), 50.4 (C-6), 48.7 (C-
9), 28.7 [1-OC(CH3)3], 18.5 (3-CH3), 19.2 and 17.9 (6-CH3 and 9-
3
CH3), 1.34 (d, J ϭ 7.1 Hz, 3 H, 3-CH3), 1.15 (s, 3 H, TiϪCH3),
3
1.01 (d, J ϭ 7.3 Hz, 3 H, 6-CH3) ppm. 13C NMR: δ ϭ 182.4 (C-
7), 172.5 (C-4), 170.0 (C-10), 158.0 (C-1), 136.0Ϫ122.0 {1-
OCH2(C6H5) and [BPh4]Ϫ}, 116.9 and 116.8 (C-Cp and C-CpЈ),
68.0 [1-OCH2(C6H5)], 53.3 (10-OCH3), 52.5 (C-3), 51.7 (TiϪCH3),
2 ϫ 49.8 (C-6 and C-9), 17.0 (3-CH3), 16.7 (9-CH3), 16.0 (6-CH3)
ppm.
1
3
CH3) ppm. Boc-8(ChelB): H NMR: δ ϭ 7.16 (br. d, J ϭ 8.8 Hz,
1 H, 8-H), 6.11 and 6.10 (2 ϫ s, 2 ϫ 5 H, Cp-H and CpЈ-H), 4.98
(br. d, 3J ϭ 5.7 Hz, 1 H, 2-H), 4.98 (q, 3J ϭ 7.3 Hz, 1 H, 6-H),
4.30 (m, 1 H, 9-H), 3.88 (m, 1 H, 3-H), 3.79 (s, 3 H, 10-OCH3),
Product Z-8(chelB): Reaction of Z-8(pept) (135 mg, 3.56·10Ϫ4 mol)
with 13 (208 mg, 3.56·10Ϫ4 mol) yielded 293 mg (94%) of Z-
8(chelB). M.p. (DSC): 79 °C (dec.). [α]D ϭ Ϫ59 (c ϭ 1.0, CH2Cl2).
1.52 (d, J ϭ 7.4 Hz, 3 H, 6-CH3), 1.43 [s, 9 H, 1-OC(CH3)3], 1.42
3
3
3
(d, J ϭ 7.7 Hz, 3 H, 9-CH3), 1.28 (d, J ϭ 8.0 Hz, 3 H, 3-CH3)
ppm. 13C NMR: δ ϭ 178.0 (C-7), 174.3 (C-4), 171.4 (C-10), 155.4
3166
Eur. J. Inorg. Chem. 2002, 3156Ϫ3171