6
Tetrahedron Letters
130.22, 129.30, 128.49, 128.12 (2C), 128.02, 127.88, 127.69, 125.38, 123.71, 72.00, 51.59, 35.27, 33.99, 26.11, 25.66, 25.59, 22.79, 20.74, 14.19;
[α]D20= +10.9 (c 1.5, benzene); Chiracel OD, 5 µm, 250 x 4.6 mm, 236 nm, Hexane/i-PrOH 95:5, 0.6 mL/min, tR = 13.8 min. Compound 12: 1H NMR
(CDCl3, 300 MHz): 5.8–5.6 (dt, J = 10.8, 7.5 Hz, 1H), 5.6–5.5 (ddt, J = 10.8, 7.2, 1.2 Hz, 1H), 5.5–5.3 (m, 7H), 5.2–5.0 (ddt, J = 10.8, 9.0, 1.5 Hz,
1H), 3.9–3.8 (m, 1H), 3.7 (dd, J = 9.0, 2.1 Hz, 1H), 3.7–3.6 (s, 3H), 3.1–2.9 (m, 2H), 3.0–2.9 (dd, J = 3.0, 2.1 Hz, 1H), 2.9–2.7 (m, 4H), 2.4–2.3 (m,
6H), 2.1–2.0 (m, 3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 75.5 MHz): 173.64, 135.15, 134.86, 129.24, 128.98, 128.30, 127.91 (2C),
127.19, 126.50, 123.07, 68.41, 61.79, 51.59, 50.74, 33.98, 31.39, 26.10, 25.66, 25.59, 22.79, 20.66, 14.14; [α]D20= +18.3 (c 0.48, benzene). Compound
13: 1H NMR (CDCl3, 300 MHz): 5.8–5.6 (dt, J = 11.1, 7.5 Hz, 1H), 5.6–5.5 (ddt, J = 10.8, 7.5, 1.5 Hz, 1H), 5.5–5.3 (m, 7H), 5.2–5.0 (ddt, J = 11.1,
9.0, 1.5 Hz, 1H), 3.8–3.6 (s and m, 5H), 3.1–2.9 (m, 2H), 3.0–2.9 (dd, J = 4.5, 2.4 Hz, 1H), 2.9–2.7 (m, 4H), 2.4–2.3 (m, 6H), 2.2–2.0 (m, 2H), 2.0–
1.9 (d, J = 6.6 Hz, 1H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 75.5 MHz): 173.61, 135.33, 134.93, 129.21, 128.98, 128.30, 127.95, 127.89,
127.19, 126.38, 122.99, 70.28, 62.23, 52.02, 51.59, 33.98, 32.59, 26.09, 25.66, 25.59, 22.79, 20.66, 14.15; [α]D20= +5.6 (c 0.29, benzene). 16(R),17(S)-
diHDHA (1): 1H NMR (CD3OD, 300 MHz): 6.7–6.5 (dd, J = 14.4, 11.1 Hz, 1H), 6.4–6.2 (m, 2H), 6.1–6.0 (br t, J = 11.1 Hz, 1H), 5.9–5.7 (dd, J =
15.0, 7.2 Hz, 1H), 5.5–5.3 (m, 7H), 4.1–3.9 (m, 1H), 3.6–3.5 (dt, J = 8.1, 4.8 Hz, 1H), 3.0–2.9 (m, 2H), 2.9–2.8 (m, 2H), 2.5–2.2 (m, 5H), 2.2–2.0 (m,
3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CD3OD, 75.5 MHz): 176.57, 134.38, 133.85, 133.81, 133.67, 131.20, 129.89, 129.82, 129.59 (2C),
129.09, 128.64, 126.31, 76.29, 75.98, 35.36, 31.84, 27.08, 26.51, 24.49, 21.68, 14.58. UV (EtOH) λmax 264, 274, 285 nm; HPLC-UV: Zorbax SB-C18,
–
1.8 µm, 50 x 2.1 mm, 274 nm, H2O/CH3OH (0.1% formic acid) 50:50–30:70, 0.2 mL/min, tR = 18.4 min; HPLC/MS (m/z): 359.3 [M-H]
.
16(S),17(S)-diHDHA (16): 1H NMR (CD3OD, 300 MHz): 6.7–6.5 (dd, J = 14.4, 11.1 Hz, 1H), 6.4–6.2 (m, 2H), 6.1–6.0 (br t, J = 11.1 Hz, 1H), 5.8–
5.7 (dd, J = 15.0, 6.9 Hz, 1H), 5.5–5.3 (m, 7H), 4.1–3.9 (m, 1H), 3.5–3.4 (dt, J = 7.8, 5.0 Hz, 1H), 3.0–2.9 (m, 2H), 2.9–2.8 (m, 2H), 2.5–2.2 (m, 5H),
2.2–2.0 (m, 3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CD3OD, 75.5 MHz): 176.25, 134.36, 134.30, 133.72, 133.48, 131.27, 129.86, 129.80,
129.60, 129.56, 129.22, 128.63, 126.26, 76.14, 75.88, 35.82, 31.71, 27.09, 26.52, 24.25, 21.64, 14.57. UV (EtOH) λmax 264, 274, 285 nm; HPLC-UV:
Zorbax SB-C18, 1.8 µm, 50 x 2.1 mm, 274 nm, H2O/CH3OH (0.1% formic acid) 50:50–30:70, 0.2 mL/min, tR = 19.9 min; HPLC/MS (m/z): 359.2 [M-
H] –. Compound 18: 1H NMR (CDCl3, 300 MHz): 7.8–7.7 (d, J = 8.5 Hz, 2H), 7.4–7.3 (d, J = 8.5 Hz, 2H), 5.5–5.3 (ddt, J = 10.5, 7.3, 1.5 Hz, 1H),
5.4–5.2 (m, 3H), 4.0 (t, J = 6.9 Hz, 2H), 3.7–3.6 (s, 3H), 2.8–2.7 (m, 2H), 2.5–2.3 (m, 6H), 2.4 (s, 3H); 13C NMR (CDCl3, 75.5 MHz): 173.46,
1
144.69, 133.11, 131.49, 129.79 (2C), 128.66, 128.21, 127.88 (2C), 123.37, 69.56, 51.55, 33.87, 27.06, 25.58, 22.73, 21.61. Compound 4: H NMR
(CDCl3, 300 MHz): 7.9–7.6 (m, 17H), 7.1–7.0 (d, J = 7.8 Hz, 2H), 5.6–5.4 (m, 1H), 5.4–5.1 (m, 3H), 3.8–3.6 (m, 2H), 3.6 (s, 3H), 2.5 (br t, J = 6.7
Hz, 2H), 2.5–2.3 (m, 2H), 2.3 (s, 3H), 2.3–2.1 (m, 4H); 13C NMR (CDCl3, 75.5 MHz): 173.44, 144.60, 138.26, 134.88 (d, J = 2.9 Hz, 3C), 133.64
(d, J = 9.8 Hz, 6C), 130.40 (d, J = 12.1 Hz, 6C), 129.82, 128.52, 128.18 (2C), 128.13, 126.81 (d, J = 14.9 Hz, 1C), 126.17 (2C), 118.35 (d, J = 85.8
Hz, 3C), 51.52, 33.71, 25.40, 22.66, 21.95 (d, J = 48.9 Hz, 1C), 21.23, 20.33 (d, J = 3.5 Hz, 1C). Compound 20: 1H NMR (CDCl3, 300 MHz): 9.7–
9.6 (d, J = 3.0 Hz, 1H), 5.6–5.4 (dtt, J = 10.8, 7.5, 1.5 Hz, 1H), 5.4–5.2 (dtt, J = 10.8, 7.2, 1.5 Hz, 1H), 4.4–4.3 (m, 1H), 4.3–4.2 (dd, J = 7.2, 3.0 Hz,
1H), 2.4–2.2 (m, 2H), 2.1–1.9 (m, 2H), 1.6 (s, 3H), 1.4 (s, 3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 75.5 MHz): 201.64, 135.02, 122.89,
1
110.55, 81.91, 78.41, 27.76, 27.43, 25.19, 20.78, 13.90. Compound 5: H NMR (CDCl3, 300 MHz): 9.6–9.5 (d, J = 8.1 Hz, 1H), 7.2–7.0 (dd, J =
15.3, 11.1 Hz, 1H), 6.6–6.4 (dd, J = 15.3, 11.1 Hz, 1H), 6.3–6.1 (m, 2H), 5.6–5.4 (dtt, J = 10.8, 7.2, 1.5 Hz, 1H), 5.4–5.2 (dtt, J = 10.8, 7.2, 1.5 Hz,
1H), 4.7–4.6 (m, 1H), 4.3–4.2 (dt, J = 7.5, 6.3 Hz, 1H), 2.4–2.1 (m, 2H), 2.1–1.9 (m, 2H), 1.5 (s, 3H), 1.4 (s, 3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C
NMR (CDCl3, 75.5 MHz): 193.63, 150.54, 140.13, 134.43, 132.27, 130.16, 123.44, 108.85, 78.33, 78.04, 28.69, 28.01, 25.43, 20.84, 14.05.
Compound 21: 1H NMR (CDCl3, 300 MHz): 6.6–6.4 (dd, J = 14.4, 10.8 Hz, 1H), 6.4–6.3 (dd, J = 15.0, 10.8 Hz, 1H), 6.3–6.1 (dd, J = 14.4, 10.8 Hz,
1H), 6.1–6.0 (br t, J = 10.8 Hz, 1H), 5.9–5.8 (dd, J = 15.0, 7.8 Hz, 1H), 5.5–5.2 (m, 7H), 4.6–4.5 (m, 1H), 4.2–4.1 (dt, J = 8.1, 6.0 Hz, 1H), 3.7–3.6 (s,
3H), 3.0–2.9 (m, 2H), 2.9–2.7 (m, 2H), 2.4–2.3 (m, 4H), 2.3–2.1 (m, 2H), 2.1–1.9 (m, 2H), 1.5 (s, 3H), 1.4 (s, 3H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C
NMR (CDCl3, 75.5 MHz): 173.54, 134.01, 133.71, 131.94, 130.89, 129.18, 128.88, 128.68, 128.60, 128.50, 127.98, 127.64, 124.11, 108.21, 79.11,
78.52, 51.56, 33.98, 28.75, 28.19, 26.21, 25.59, 25.57, 22.80, 20.79, 14.12. 16(R),17(S)-diHDHA methyl ester (22): 1H NMR (CDCl3, 300 MHz):
6.6–6.5 (dd, J = 14.7, 11.1 Hz, 1H), 6.5–6.3 (dd, J = 14.7, 10.8 Hz, 1H), 6.3–6.1 (dd, J = 14.7, 10.8 Hz, 1H), 6.1–6.0 (br t, J = 11.1 Hz, 1H), 5.8–5.7
(dd, J = 14.7, 7.2 Hz, 1H), 5.6–5.5 (dtt, J = 10.5, 7.2, 1.5 Hz, 1H), 5.5–5.3 (m, 6H), 4.3–4.1 (m, 1H), 3.8–3.6 (m, 1H), 3.6 (s, 3H), 3.0–2.9 (m, 2H),
2.9–2.7 (m, 2H), 2.4–2.3 (m, 4H), 2.3–2.1 (m, 2H), 2.1–1.9 (m, 2H), 1.0–0.9 (t, J = 7.5 Hz, 3H); 13C NMR (CDCl3, 75.5 MHz): 173.63, 135.27,
133.26, 131.95, 130.88, 130.68, 129.18, 128.68, 128.53, 128.49, 127.94, 127.60, 124.06, 74.93, 73.95, 51.60, 33.98, 29.99, 26.24, 25.60, 22.81, 20.72,
14.21.
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