2,2Ј:6Ј,2ЈЈ-Terpyridines Disubstituted in Positions 6 and 6ЈЈ
NMR (CDCl3): δ = 14.1 (CH3 of Et group), 18.7 (CH3 of alanine s, 1 H, NHc), 7.55–7.65 (m, 6 H, 10-H, H11, 5-H, 5ЈЈ-H), 7.74 (part
residue), 48.7 (C-14ЈЈ), 61.7 (CH2 of Et group), 76.6 (C-8), 83.1 (C-
A of an AB system, J = 8.2 Hz, 2 H, 10ЈЈ-H), 7.86 (part B of an
7), 87.9 (C-8ЈЈ), 91.1 (C-7ЈЈ), 120.7 (C-3ЈЈ), 121.0 (C-5), 121.8 (C- AB system, J = 8.2 Hz, 2 H, 11ЈЈ-H), 7.87 (t, J = 7.8 Hz, 1 H, 4-
3Ј and C-5Ј), 125.9 (C-9ЈЈ), 127.1 (C-11ЈЈ), 127.5 (C-3 and C-5ЈЈ),
132.2 (C-10ЈЈ), 134.0 (C-12ЈЈ), 137.0 (C-4 and C-4ЈЈ), 137.9 (C-4Ј),
H), 7.90 (t, J = 7.8 Hz, 1 H, 4ЈЈ-H), 7.99 (t, J = 7.8 Hz, 1 H, 4Ј-
H), 8.49 (br. s, 1 H, NHa), 8.58 (d, J = 7.8 Hz, 3 H, 3-H, 3Ј-H, 5Ј-
141.7 (C-2), 142.4 (C-6ЈЈ), 154.5 (C-2Ј), 154.6 (C-6Ј), 156.6 (C-6), H), 8.62 (d, J = 7.8 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR (CDCl3): δ =
156.7 (C-2ЈЈ), 165.9 (C-13ЈЈ), 173.2 (CO2Et) ppm. C31H24N4O3 14.0 (CH3 of Et group), 28.3 (CH3 of tBu group), 42.0 (C-14ЈЈ),
(500.6): calcd. C 74.38, H 4.83, N 11.19; found C 74.59, H 5.00, N
11.05.
45.9 (C-14), 61.8 (CH2 of Et group), 81.2 (quaternary C of tBu
group), 87.5 (C-8ЈЈ), 88.8 (C-7 and C-8), 91.0 (C-7ЈЈ), 119.0 (C-9),
119.4 (C-11), 120.3 (C-3), 120.7 (C-3ЈЈ), 121.8 (C-3Ј and C-5Ј),
126.0 (C-9ЈЈ), 127.1 (C-11ЈЈ), 127.3 (C-5ЈЈ), 127.5 (C-5), 132.3 (C-
10ЈЈ), 133.0 (C-10), 133.7 (C-12ЈЈ), 137.0 (C-4ЈЈ), 137.1 (C-4), 138.0
(C-12 and C-4Ј), 142 (C-6ЈЈ), 143.0 (C-6), 155.0 (C-2Ј and C-6Ј),
156.8 (CO2tBu), 157.0 (C2 and C-2ЈЈ), 166.3 (C-13ЈЈ), 168.0 (C-13),
170.2 (CO2Et) ppm. C43H38N6O6 (734.8): calcd. C 70.28, H 5.21,
N 11.44; found C 70.30, H 5.44, N 11.61.
Adduct 5c (215 mg) was obtained in 65% yield; m.p. 191–193 °C.
1
IR (chloroform): ν = 3300, 1735, 1650 cm–1. H NMR (CDCl ): δ
˜
3
= 1.05 (d, J = 6.8 Hz, 3 H, CH3 of iPr), 1.07 (d, J = 6.8 Hz, 3 H,
CH3 of iPr), 1.34 (t, J = 7.1 Hz, 3 H, CH3 of Et group), 2.30 (m,
1 H, CH of iPr), 3.25 (s, 1 H, 8-H), 4.26 (q, J = 7.1 Hz, 2 H, CH2
of Et group), 4.78 (dd, J = 6.0, 7.0 Hz, 1 H, 14ЈЈ-H), 6.73 (d, J =
6.0 Hz, 1 H, NHc), 7.54 (d, J = 7.6 Hz, 1 H, 5-H), 7.64 (d, J =
7.6 Hz, 1 H, 5ЈЈ-H), 7.75 (part A of an AB system, J = 8.4 Hz, 2
H, 10ЈЈ-H), 7.88 (part B of an AB system, J = 8.4 Hz, 2 H, 11ЈЈ-
H), 7.92 (t, J = 7.6 Hz, 1 H, 4ЈЈ-H), 8.01 (t, J = 7.6 Hz, 1 H, 4Ј-
Adduct 6b (172 mg) was obtained in 50% yield; m.p. 237 °C. [α]D
= +11.5 (c = 0.15, in chloroform). IR (nujol): ν˜ = 3297, 1738, 1695,
1
1662 cm–1. H NMR (CDCl3): δ = 1.34 (t, J = 7.0 Hz, 3 H, CH3
H), 8.59 (d, J = 7.6 Hz, 1 H, 5Ј-H), 8.63 (d, J = 7.6 Hz, 2 H, 3-H, of Et group), 1.46 (d, J = 7.1 Hz, 3 H, CH3CH of N-Boc-protected
3ЈЈ-H), 8.64 (d, J = 7.6 Hz, 1 H, 3Ј-H) ppm. 13C NMR (CDCl3): δ alanine), 1.50 (s, 9 H, CH3 of tBu group), 1.56 (d, J = 7.1 Hz, 3
= 14.2 (CH3 of Et group), 17.9 (CH3 of iPr), 19.0 (CH3 of iPr),
31.7 (CH of iPr), 57.5 (C-14ЈЈ), 61.5 (CH2 of Et group), 77.0 (C-
8), 83.0 (C-7), 88.8 (C-8ЈЈ), 91.5 (C-7ЈЈ), 120.8 (C-3 and C-3ЈЈ),
H, CH3CH of alanine Et ester), 4.27 (q, J = 7.1 Hz, 2 H, CH2 of
Et group), 4.34 (br. q, J = 7.0 Hz, 2 H, 14-H), 4.80 (q, J = 7.1 Hz,
2 H, 14ЈЈ-H), 5.10 (br. d, J = 7.0 Hz, 1 H, NHb), 6.88 (d, J =
121.9 (C-5Ј and C-3Ј), 126.0 (C-9ЈЈ), 127.1 (C-11ЈЈ), 127.6 (C-5 and 7.0 Hz, 1 H, NHc), 7.55 (d, J = 7.8 Hz, 1 H, 3-H), 7.58 (AB system,
C-5ЈЈ), 132.3 (C-10ЈЈ), 134.0 (C-12ЈЈ), 137.1 (C-4), 137.2 (C-4ЈЈ), J = 8.3 Hz, 4 H, 10-H, 11-H), 7.61 (d, J = 7.8 Hz, 1 H, 5ЈЈ-H),
138.0 (C-4Ј), 142.0 (C-6ЈЈ), 142.5 (C-6), 154.5 (C-2ЈЈ), 155.5 (C-2Ј 7.72 (part A of an AB system, J = 8.3 Hz, 2 H, 10ЈЈ-H), 7.85 (part
and C-6Ј), 157.0 (C-2), 167.0 (C-13ЈЈ), 172.0 (CO2Et) ppm.
C33H28N4O3 (528.6): calcd. C 74.98, H 5.34, N 10.60; found C
75.11, H 5.45, N 10.35.
B of an AB system, J = 8.3 Hz, 2 H, 11ЈЈ-H), 7.86 (t, J = 7.8 Hz,
1 H, 4-H), 7.89 (t, J = 7.8 Hz, 1 H, 4ЈЈ-H), 7.98 (t, J = 7.8 Hz, 1
H, 4Ј-H), 8.56 (d, J = 7.8 Hz, 1 H, 5-H), 8.59 (d, J = 7.8 Hz, 2 H,
3Ј-H, 5Ј-H), 8.62 (d, J = 7.8 Hz, 2 H, 3ЈЈ-H), 8.81 (br. s, 1 H, NHa)
ppm. 13C NMR (CDCl3): δ = 14.2 (CH3 of Et group), 17.3
(CH3CH of N-Boc-protected alanine), 18.6 (CH3CH of alanine Et
ester), 28.3 (CH3 of tBu group), 48.7 (C-14ЈЈ), 50.9 (C-14), 61.7
(CH2 of Et group), 81.0 (quaternary C of tBu group), 87.9 (C-8ЈЈ),
88.65 (C-7), 89.0 (C-8), 91.1 (C-7ЈЈ), 117.8 (C-12), 118.6 (C-9),
119.4 (C-11), 120.2 (C-5), 120.7 (C-3ЈЈ), 121.8 (C-3Ј and C-5Ј),
125.8 (C-9ЈЈ), 127.1 (C-11ЈЈ), 127.3 (C-5ЈЈ), 127.5 (C-3), 132.2 (C-
10ЈЈ), 132.9 (C-10), 134.0 (C-12ЈЈ), 137.0 (C-4 and C-4ЈЈ), 138.0
(C-4Ј), 142.4 (C-6ЈЈ), 143.0 (C-2), 154.6 (C-6Ј), 154.7 (C-2Ј), 156.5
(CO2tBu), 156.7 (C-6 and C-2Ј), 167.0 (C-13ЈЈ), 171.0 (C-13), 174.0
(CO2Et) ppm. C45H42N6O6 (762.9): calcd. C 70.85, H 5.55, N
11.02; found C 70.80, H 5.41, N 11.29.
Synthesis of Adducts 6a–c. General Procedure: A stirred solution of
tpy 5 (0.45 mmol) and Boc-amino acid N-(4-iodophenyl)amide 4
(0.70 mmol) in a mixture of diisopropylamine (30 mL) and dry
THF (37 mL) was degassed with a nitrogen stream for 10 min. To
this solution CuI (10 mg, 0.047 mmol) and [PdCl2(PPh3)2] (8 mg,
0.014 mmol) were added, and the mixture was heated to 80 °C un-
der a positive pressure of nitrogen for 15 h. Upon cooling, a brown
solid had formed, which was removed by filtration. The filtrate
was then concentrated under vacuum, and the resulting residue was
purified by flash chromatography with a DCM/MeOH (98:2) mix-
ture as eluant to afford the product as an orange solid. See Figure 4
for NMR numbering.
Adduct 6c (203 mg) was obtained in 55% yield; m.p. 220 °C. [α]D
= +10.9 (c = 0.23, in chloroform). IR (nujol): ν = 3273, 1738, 1695,
˜
1
1662 cm–1. H NMR (CD3CN): δ = 1.02 (d, J = 7.0 Hz, 6 H, CH3
of iPr group of N-Boc-protected valine), 1.08 (d, J = 7.0 Hz, 6 H,
CH3 of iPr group of valine Et ester), 1.34 (t, J = 6.9 Hz, 3 H, CH3
of Et group), 1.49 (s, 9 H, CH3 of tBu group), 2.30 (m, 2 H, CH
of iPr groups), 4.01 (dd, J = 7.0 Hz and 6.0, 1 H, 14-H), 4.26 (AB
system, J = 6.9 Hz and 2.6, 2 H, CH2 of Et group), 4.80 (dd, J =
7.0 Hz and 4.0, 1 H, 14ЈЈ-H), 5.10 (br. d, J = 6.0 Hz, 1 H, NHb),
6.70 (d, J = 4.0 Hz, 1 H, NHc), 7.59 (d, J = 7.8 Hz, 1 H, 3-H), 7.61
(AB system, J = 7.0 Hz, 4 H, 10-H, 11-H), 7.63 (d, J = 7.8 Hz, 1
H, 5ЈЈ-H), 7.79 (A part of an AB system, J = 8.5 Hz, 2 H, 10ЈЈ-H),
7.85 (B part of an AB system, J = 8.5 Hz, 2 H, 11ЈЈ-H), 7.87 (t, J
= 7.8 Hz, 1 H, 4-H), 8.08 (t, J = 7.8 Hz, 1 H, 4Ј-H), 8.25 (br. s, 1
H, NHa), 8.58 (d, J = 7.8 Hz, 1 H, 5-H), 8.60 (d, J = 7.8 Hz, 2 H,
3Ј-H and 5Ј-H), 8.63 (d, J = 7.8 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR
Figure 4. Numbering for adducts 6a–c.
Adduct 6a (169 mg) was obtained in 51% yield; m.p. 222–223 °C.
IR (nujol): ν = 3348, 1740, 1690, 1665 cm–1. H NMR (CDCl ): δ (CD3CN): δ = 14.2 (CH3 of Et group), 18.0 (one CH3 of iPr group
1
˜
3
= 1.35 (t, J = 7.0 Hz, CH3 of Et group), 1.51 (s, 9 H, CH3 of tBu
group), 3.93 (d, J = 5.8 Hz, 2 H, 14-H), 4.20–4.35 (m, 4 H, 14ЈЈ-
H, CH2 of Et group), 5.30 (br. t, J = 5.8 Hz, 1 H, NHb), 6.75 (br.
of valine Et ester), 19.0 (one CH3 of iPr group of valine Et ester),
19.1 (one CH3 of iPr group of N-Boc-protected valine), 19.5 (one
CH3 of iPr group of N-Boc-protected valine), 28.3 (CH3 of tBu
Eur. J. Org. Chem. 2008, 3976–3983
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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