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Y. Sugiyama et al.
Paper
Synthesis
HRMS (FAB): m/z [M + H]+ calcd for C18H36N3O4S: 390.2428; found:
390.2379.
1H NMR (270 MHz, CDCl3): δ = 0.88–0.94 (m, 6 H), 1.33 (d, J = 6.5 Hz, 3
H), 1.43–1.52 (m, 11 H), 1.56–1.66 (m, 5 H), 1.77–1.89 (m, 4 H), 2.99–
3.13 (m, 2 H), 3.44–3.52 (m, 1 H), 4.40–4.48 (m, 1 H), 4.55–4.62 (m, 1
H), 4.78–4.82 (m, 1 H), 5.12 (d, J = 13.2 Hz, 1 H), 5.19 (d, J = 12.4 Hz, 1
H), 6.90 (d, J = 7.8 Hz, 1 H), 7.34 (s, 5 H), 7.77 (d, J = 8.4 Hz, 1 H).
13C NMR (67.8 MHz, CDCl3): δ = 21.6, 22.4, 22.7, 24.8, 28.4 (3 C), 29.3,
31.7, 39.9, 40.9, 50.6, 50.9, 52.3, 65.2, 67.0, 79.0, 126.9–128.5 (5 C),
135.4, 156.1, 171.6, 172.5, 175.9.
Ala-Ile-Tyr(Bn)-OBn
Ala-Ile-Tyr(Bn)-OBn was prepared from f3-Fmoc-Ala-Ile-Tyr(Bn)-OBn
(45.0 mg, 0.039 mmol) in 81% yield (17.2 mg) by following the proce-
dure used for the preparation of Ala-Ala-Ala-OBn; white solid; mp
140.2–141.1 °C.
HRMS (FAB): m/z [M + H]+ calcd for C27H45N4O6: 521.3341; found:
521.3389.
1H NMR (270 MHz, CDCl3): δ = 0.80–0.89 (m, 6 H), 1.01–1.17 (m, 1 H),
1.31 (d, J = 7.3 Hz, 3 H), 1.37–1.52 (m, 1 H), 1.75 (br s, 2 H), 1.83–1.96
(m, 1 H), 2.97–3.10 (m, 2 H), 3.40–3.49 (m, 1 H), 4.20–4.25 (m, 1 H),
4.83–4.90 (m, 1 H), 5.00 (s, 2 H), 5.07 (d, J = 11.8 Hz, 1 H), 5.16 (d, J =
11.8 Hz, 1 H), 6.49 (d, J = 7.8 Hz, 1 H), 6.81 (d, J = 8.6 Hz, 2 H), 6.93 (d,
J = 8.6 Hz, 2 H), 7.26–7.44 (m, 10 H), 7.73 (d, J = 9.2 Hz, 1 H).
13C NMR (67.8 MHz, CDCl3): δ = 11.2, 15.4, 21.7, 24.8, 36.8, 37.0, 50.7,
53.1, 57.2, 67.2, 69.9, 114.9 (2 C), 127.4–130.4 (13 C), 135.1, 137.0,
157.8, 170.9, 171.1, 175.7.
Phe-Lys(Boc)-Leu-OBn
Phe-Lys(Boc)-Leu-OBn was prepared from f4-Fmoc-Phe-Lys(Boc)-
Leu-OBn (40.0 mg, 0.031 mmol) in 88% yield (16.1 mg) as a yellow oil
by following the procedure used for the preparation of Ala-Ala-Ala-
OBn.
1H NMR (270 MHz, CDCl3): δ = 0.88–0.92 (m, 6 H), 1.26–1.34 (m, 2 H),
1.43–1.49 (m, 12 H), 1.54–1.69 (m, 5 H), 1.78–1.88 (m, 1 H), 2.70–2.78
(m, 1 H), 3.02–3.13 (m, 2 H), 3.20–3.26 (m, 1 H), 3.60–3.64 (m, 1 H),
4.38–4.46 (m, 1 H), 4.55–4.64 (m, 1 H), 4.69–4.74 (m, 1 H), 5.12 (d, J =
12.7 Hz, 1 H), 5.19 (d, J = 12.4 Hz, 1 H), 6.72 (d, J = 7.8 Hz, 1 H), 7.20–
7.34 (m, 10 H), 7.81 (d, J = 7.8 Hz, 1 H).
13C NMR (67.8 MHz, CDCl3): δ = 21.7 (2 C), 22.4, 22.7 (2 C), 24.8 (2 C),
28.4 (3 C), 29.3, 40.9, 50.9, 52.5, 56.1, 67.1 (2 C), 127.0–129.3 (10 C),
135.3 (2 C), 156.1, 171.4, 172.5, 174.0.
HRMS (FAB): m/z [M + H]+ calcd for C33H49N4O6: 597.3654; found:
597.3669.
HRMS (FAB): m/z [M + H]+ calcd for C32H40N3O5: 546.2970; found:
546.2948.
Phe-Ile-Tyr(Bn)-OBn
Phe-Ile-Tyr(Bn)-OBn was prepared from f4-Fmoc-Phe-Ile-Tyr(Bn)-OBn
(40.0 mg, 0.030 mmol) in 92% yield (17.1 mg) as a yellow oil by fol-
lowing the procedure used for the preparation of Ala-Ala-Ala-OBn.
1H NMR (270 MHz, CDCl3): δ = 0.77–0.88 (m, 6 H), 0.97–1.13 (m, 1 H),
1.34–1.49 (m, 3 H), 1.81–1.91 (m, 1 H), 2.65–2.73 (m, 1 H), 2.97–3.05
(m, 2 H), 3.20–3.26 (m, 1 H), 3.53–3.58 (m, 1 H), 4.20–4.26 (m, 1 H),
4.84–4.93 (m, 1 H), 4.99 (s, 2 H), 5.09 (d, J = 11.8 Hz, 1 H), 5.16 (d, J =
11.8 Hz, 1 H), 6.43 (d, J = 7.8 Hz, 1 H), 6.81 (d, J = 8.6 Hz, 2 H), 6.94 (d,
J = 8.6 Hz, 2 H), 7.20–7.38 (m, 15 H), 7.80 (d, J = 9.2 Hz, 1 H).
13C NMR (67.8 MHz, CDCl3): δ = 11.2, 15.4, 24.8, 36.7, 37.0, 40.8, 53.1,
56.3, 57.3, 67.2, 69.9, 114.8 (2 C), 126.8–130.4 (19 C), 135.0, 136.9,
137.6, 157.8, 170.7, 171.1, 174.2.
HRMS (FAB): m/z [M + H]+ calcd for C38H44N3O5: 622.3283; found:
622.3263.
Leu-Lys(Boc)-Leu-OBn
Leu-Lys(Boc)-Leu-OBn was prepared from f6-Fmoc-Leu-Lys(Boc)-Leu-
OBn (50.0 mg, 0.027 mmol) in 91% yield (13.9 mg) as a yellow oil by
following the procedure used for the preparation of Ala-Ala-Ala-OBn.
1H NMR (270 MHz, CDCl3): δ = 0.89–0.96 (m, 12 H), 1.26–1.43 (m, 17
H), 1.58–1.71 (m, 5 H), 1.80–1.88 (m, 1 H), 3.01–3.11 (m, 2 H), 3.52–
3.58 (m, 1 H), 4.45–4.48 (m, 1 H), 4.54–4.61 (m, 1 H), 4.77–4.82 (m, 1
H), 5.11 (d, J = 12.4 Hz, 1 H), 5.18 (d, J = 12.4 Hz, 1 H), 6.82 (d, J = 6.5
Hz, 1 H), 7.34 (s, 5 H), 7.71 (d, J = 8.3 Hz, 1 H).
Leu-Ile-Tyr(Bn)-OBn
13C NMR (67.8 MHz, CDCl3): δ = 21.5, 21.7 (2 C), 22.5, 22.7 (2 C), 23.1,
24.7, 24.8 (2 C), 28.6 (3 C), 29.4, 31.8, 40.8, 51.0, 53.2, 67.1, 79.1,
128.2–128.6 (5 C), 135.4, 156.2, 171.6, 172.5, 173.7.
Leu-Ile-Tyr(Bn)-OBn was prepared from f6-Fmoc-Leu-Ile-Tyr(Bn)-OBn
(40.0 mg, 0.027 mmol) in 93% yield (14.6 mg) as a white solid by fol-
lowing the procedure used for the preparation of Ala-Ala-Ala-OBn;
white solid; mp 128.1–129.1 °C.
HRMS (FAB): m/z [M + H]+ calcd for C30H51N4O6: 563.3810; found:
1H NMR (270 MHz, CDCl3): δ = 0.83–0.97 (m, 12 H), 1.03–1.14 (m, 1
H), 1.26–1.45 (m, 2 H), 1.51 (br s, 2 H), 1.62–1.73 (m, 2 H), 1.84–1.92
(m, 1 H), 3.00–3.05 (m, 2 H), 3.32–3.37 (m, 1 H), 4.19–4.25 (m, 1 H),
4.83–4.90 (m, 1 H), 5.00 (s, 2 H), 5.07 (d, J = 12.4 Hz, 1 H), 5.16 (d, J =
12.4 Hz, 1 H), 6.43 (d, J = 7.8 Hz, 1 H), 6.81 (d, J = 8.6 Hz, 2 H), 6.94 (d,
J = 8.6 Hz, 2 H), 7.26–7.41 (m, 10 H), 7.78 (d, J = 9.5 Hz, 1 H).
13C NMR (67.8 MHz, CDCl3): δ = 11.2, 15.5, 21.3, 23.4, 24.7, 24.9, 36.8,
37.1, 44.0, 53.1, 53.5, 57.2, 67.2, 69.9, 114.9 (2 C), 127.4–130.4 (13 C),
135.1, 136.9, 157.8, 170.8, 171.1, 175.6.
563.3810.
Ala-Lys(Boc)-Pro-OBn
Ala-Lys(Boc)-Pro-OBn was prepared from f3-Fmoc-Ala-Lys(Boc)-Pro-
OBn (40.0 mg, 0.036 mmol) in quantitative yield (18.1 mg) as a yellow
oil by following the procedure used for the preparation of Ala-Ala-
Ala-OBn.
1H NMR (270 MHz, CDCl3): δ = 1.32–1.43 (m, 16 H), 1.60–1.66 (m, 1
H), 1.80 (br s, 2 H), 1.93–2.06 (m, 4 H), 2.18–2.27 (m, 1 H), 3.03–3.13
(m, 2 H), 3.44–3.52 (m, 1 H), 3.59–3.68 (m, 1 H), 3.76–3.84 (m, 1 H),
4.55–4.60 (m, 1 H), 4.68–4.75 (m, 1 H), 4.82–4.86 (m, 1 H), 5.11 (d, J =
12.4 Hz, 1 H), 5.22 (d, J = 12.7 Hz, 1 H), 7.34 (s, 5 H), 7.82 (d, J = 8.6 Hz,
1 H).
HRMS (FAB): m/z [M + H]+ calcd for C35H46N3O5: 588.3439; found:
588.3481.
Ala-Lys(Boc)-Leu-OBn
13C NMR (67.8 MHz, CDCl3): δ = 21.6, 21.9, 24.9, 28.4 (3 C), 28.9 (2 C),
29.3, 31.9, 40.4, 47.0, 49.9, 50.7, 58.9, 67.0, 128.1–128.5 (5 C), 135.5,
156.0, 170.8, 171.8, 175.5.
Ala-Lys(Boc)-Leu-OBn was prepared from f3-Fmoc-Ala-Lys(Boc)-Leu-
OBn (40.0 mg, 0.035 mmol) in 84% yield (15.5 mg) as a yellow oil by
following the procedure used for the preparation of Ala-Ala-Ala-OBn.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–R