Fumuquinazoline K (1): HR ESI-MS m/z 435.1670 [M+H]+ (calcd. for C23H23N4O5 435.1663); 457.1484 [M+Na]+ (calcd. for C23H22NaN4O5 457.1482); -3.5° (0.1, c, MeOH); UV (MeOH) λmax (log ε): 210 (0.74), 230 (0.52) nm; IR (film) vmax: 3356, 1724, 1666, 1608, 1479cm-1; 1H NMR (500MHz, DMSO-d6) δ: 8.29 (1H, s, H-25), 8.18 (1H, s, H-19), 7.88 (1H, td, J=8.5, 1.5Hz, H-21), 7.70 (1H, d, J=8.0Hz, H-22), 7.59 (1H, t, J=7.5Hz, H-20), 7.51 (1H, d, J=8.0Hz, H-8), 7.50 ( 1H, d, J=7.5Hz, H-5), 7.44 (1H, td, J=7.5, 1.0Hz, H-7), 7.26 (1H, td, J=7.5, 1.0Hz, H-6), 5.92 (1H, s, H-14), 5.61 (1H, s, H-2), 4.63 (1H, q, J=7.0Hz, H-11), 3.17 (3H, s, H-27), 2.96 (1H, t, J=7.5Hz, H-13a), 2.54 (1H, m, H-13b), 1.61 (3H, d, J=6.5Hz, H-12). 13C NMR (125MHz, DMSO-d6) δ: 172.0 (C, C-10), 165.7 (C, C-17), 160.0 (C, C-15), 147.4 (C, C-23), 146.6 (C, C-25), 138.7 (C, C-9), 136.7 (C, C-4), 134.7 (CH, C-21), 129.9 (CH, C-7), 127.3 (CH, C-20), 127.2 (CH, C-22), 126.4 (CH, C-19), 125.5 (CH, C-6), 124.9 (CH, C-5), 121.2 (C, C-18), 114.5 (CH, C-8), 82.5 (CH, C-2), 76.4 (C, C-3), 59.8 (CH, C-14), 50.4 (CH, C-11), 48.6 (CH3, C-27), 39.0 (CH2, C-13), 14.0 (CH3, C-12).
X-ray crystal data for compound 1: chemical formulae C23H24N4O6, F.W=434.44, white color crystals, 0.15×0.11×0.1mm3, trigonal, space group: P3121, Å, a=10.7396 (4) Å, b=10.7396 (4) Å, c=35.6809 (12) Å, α=β=90°, γ=120°. V=3564.0 (3) Å3, Z=6, Dc=1.214g/cm3, F(000)=1368.0, Cu Kα radiation, λ=1.54184, θ range for data collection: 7.432 to 148.206°; 8851 reflections collected, 4382 unique (Rint=0.0564), the structure was refined by full-matrix least-squares on F2. Final GoF=1.047. Final R indexes [I>2σ (I)]: R1=0.0793, wR2=0.2256. Final R indexes (all data) R1=0.0.0846, wR2=0.2360; Flack Parameters=-0.5 (3); Largest diff. peak and hole: 0.48 and -0.48eÅ-3. Data were collected on Agilent Xcalibur Nova single-crystal diffractometer using Cu Kα radiation. The crystal structure was refined by full-matrix least-squares calculation. Crystallographic data for the structure of 1 have been deposited in the Cambridge Crystallographic Data Centre (deposition number: CCDC 1847139).
Chaetominine (2): ESI-MS m/z: 403 [M+H]+; 1H NMR (700MHz, CD3OD) δ: 8.23 (1H, brs, H-24), 8.13 (1H, s, H-19), 7.81 (1H, t, J=7.7Hz, H-21), 7.70 (1H, d, J=7.5Hz, H-22), 7.52 (1H, t, J=7.0Hz, H-20), 7.45 (1H, d, J=8.4Hz, H-5), 7.37 (1H, t, J=7.7Hz, H-8), 7.20 (1H, t, J=7.7Hz, H-6), 5.88 (1H, s, H-12), 5.55 (1H, s, H-2), 4.55 (1H, q, J=14.0, 6.3Hz, H-24), 2.88 (1H, t, J=12.6Hz, H-13a), 2.47 (1H, d, J=11.9Hz, H-13b), 1.55 (1H, d, J=2.8Hz, H-26). 13C NMR (150MHz, CD3OD) δ: 172.0 (C, C-25), 165.6 (C, C-15), 160.0 (C, C-11), 147.4 (C, C-23), 146.8 (C, C-21), 138.7 (C, C-9), 134.7 (CH, C-4, C-19), 129.9 (CH, C-7), 127.3 (CH, C-17), 127.2 (CH, C-18), 126.4 (CH, C-20), 125.5 (CH, C-6), 124.9 (CH, C-5), 120.9 (C, C-16), 114.5 (CH, C-8), 82.5 (CH, C-2), 76.4 (C, C-3), 59.6 (CH, C-24), 50.1 (CH, C-14), 38.2 (CH2, C-13), 14.0 (CH3, C-12).
3'-(4-oxoquinazolin-3-yl) spiro[5'-oxolane]-2, 2'-dione (3): Pale yellow oil; ESI-MS m/z: 348 [M+H]+; 1H NMR (700MHz, CDCl3) δ: 8.64 (1H, s, H-22), 8.29 (1H, d, J=7.7Hz, H-16), 7.90 (1H, t, J=7.7Hz, H-18), 7.77 (1H, d, J=7.0Hz, H-5), 7.76 (1H, d, J=8.6Hz, H-19), 7.75 (1H, d, J=7.7Hz, H-17), 7.40 (1H, t, J=7.7Hz, H-7), 7.19 (1H, t, J=7.7Hz, H-6), 7.02 (1H, d, J=7.7Hz, H-8), 5.70 (1H, t, J=10.5Hz, H-11), 3.25 (1H, dd, J=14.0, 10.5Hz, H-12a), 3.11 (1H, dd, J=14.0, 4.2Hz, H-12b). 13C NMR (150MHz, CDCl3) δ: 175.4 (C, C-2), 171.1 (C, C-10), 160.1 (C, C-14), 147.2 (CH, C-22), 147.2 (C, C-20), 142.6 (C, C-9), 134.6 (CH, C-18), 131.4 (CH, C-7), 127.6 (CH, C-17), 127.3 (CH, C-19), 126.7 (C, C-4), 126.1 (CH, C-16), 125.4 (CH, C-5), 123.1 (CH, C-6), 121.9 (C, C-15), 110.5 (CH, C-8), 80.7 (C, C-3), 57.2 (CH, C-11), 33.7 (CH2, C-12).
Fumiquinazoline J (4): ESI-MS m/z: 357 [M+H]+; 1H NMR (700MHz, DMSO-d6) δ: 9.58 (1H, s, H-19), 8.15 (1H, dd, J=8.0, 1.0Hz, H-10), 7.81 (1H, td, J=7.8, 7.3Hz, H-8), 7.64 (1H, d, J=8.0Hz, H-7), 7.53 (1H, td, J=7.8, 7.5Hz, H-9), 7.41 (1H, d, J=8.0Hz, H-24), 7.38 (1H, d, J=8.5Hz, H-21), 7.11 (1H, td, J=8.0, 7.0Hz, H-22), 7.00 (1H, td, J=7.5, 7.0Hz, H-22), 5.71 (1H, br, H-14), 3.44 (1H, dd, J=17.5, 3.5Hz, H-15a), 3.24 (1H, dd, J=18.0, 4.5Hz, H-15b), 2.12 (3H, s, H-16). 13C NMR (150MHz, DMSO-d6) δ: 169.2 (C, C-1), 159.4 (C, C-12), 154.4 (C, C-4), 146.7 (C, C-6), 134.9 (CH, C-8), 134.0 (C, C-18, C-20), 127.4 (CH, C-7, C-9), 127.3 (C, C-25), 126.4 (CH, C-10), 122.3 (CH, C-22), 120.2 (C, C-11), 119.4 (CH, C-23), 118.2 (CH, C-24), 111.8 (CH, C-21), 105.6 (C, C-17), 54.6 (C, C-3), 54.2 (CH, C-14), 25.6 (CH2, C-15), 18.4 (CH3, C-16).
Fumitremorgin C (5): ESI-MS m/z: 380 [M+H]+; 1H NMR (700MHz, CDCl3) δ: 7.94 (1H, s, H-1), 7.43 (1H, d, J=8.6Hz, H-16), 6.85 (1H, d, J=2.1Hz, H-19), 6.82 (1H, d, J=9.1Hz, H-17), 5.98 (1H, d, J=9.5Hz, H-3), 4.83 (1H, m, H-6), 4.18 (1H, dd, J=11.6, 4.9Hz, H-6), 4.05 (1H, m, H-12), 3.83 (3H, s, OCH3-18), 3.60 (2H, m, H-9), 3.44 (2H, m, H-15), 3.10 (dd, J=15.8, 11.6Hz, H-13), 2.34 (1H, m, H-7a), 2.23 (1H, d, J=1.9Hz, H-7b), 2.06 (1H, dd, J=7.2, 4.1Hz, H-8a), 1.94 (1H, d, J=8.7Hz, H-8b), 1.94 (3H, d, J=0.8Hz, H-23), 1.64 (3H, d, J=0.8Hz, H-24). 13C NMR (150MHz, CDCl3) δ: 169.6 (C, C-5), 165.8 (C, C-11), 156.5 (C, C-18), 137.1 (C, C-20), 134.0 (C, C-22), 132.2 (C, C-2), 124.2 (CH, C-21), 120.8 (C, C-15), 118.9 (CH, C-16), 109.5 (CH, C-17), 106.2 (C, C-14), 95.3 (CH, C-19), 59.3 (CH, C-6), 56.8 (CH, C-12), 55.8 (CH3, C-25), 51.0 (CH, C-3), 45.4 (CH2, C-9), 30.6 (CH2, C-7), 28.6 (CH2, C-7), 25.7 (CH3, C-23), 23.1 (CH2, C-8), 22.0 (CH2, C-13), 18.1 (CH3, C-24).
Spirotryprostatin A (6): ESI-MS m/z: 396 [M+H]+; 1H NMR (700MHz, CD3OD) δ: 7.04 (1H, d, J=8.4Hz, H-4), 6.56 (1H, dd, J=8.4, 2.1Hz, H-5), 6.50 (1H, d, J=2.1Hz, H-7), 5.11 (1H, dt, J=9.1, 1.4Hz, H-19), 5.04 (1H, dd, J=12.5, 7.7Hz, H-9), 4.73 (1H, d, J=9.1Hz, H-18), 4.45 (1H, t, J=7.7Hz, H-12), 3.80 (3H, s, OMe-6), 3.57 (1H, m, H-15), 2.61 (1H, dd, J=13.3, 9.5Hz, H-8a), 2.35 (1H, dd, J=13.3, 10.1Hz, H-8b), 2.33 (1H, m, H-13a), 2.14 (1H, m, H-13b), 2.06 (1H, m, H-14a), 2.03 (1H, m, H-14b), 1.67 (3H, d, J=0.7Hz, H-21), 1.20 (3H, d, J=8.4Hz, H-22). 13C NMR (150MHz, CD3OD) δ: 183.2 (C, C-2), 169.5 (C, C-11), 168.9 (C, C-17), 162.2 (C, C-6), 144.4 (C, C-7a), 139.1 (C, C-20), 128.2 (CH, C-4), 122.7 (CH, C-19), 120.1 (C, C-3a), 107.7 (CH, C-5), 97.7 (CH, C-7), 62.3 (CH, C-9), 61.8 (CH, C-12), 59.8 (CH, C-18), 57.1 (C, C-3), 55.9 (C, OCH3-6), 46.2 (CH2, C-14), 35.3 (CH2, C-8), 28.5 (CH2, C-13), 25.6 (CH3, C-22), 24.5 (CH2, C-15), 18.1 (CH3, C-21).
Brevianamide F (7): ESI-MS m/z: 284 [M+H]+; -75.3° (c 0.1 MeoH); 1H NMR (500MHz, CD3OD) δ: 7.75 (1H, s, NH-1), 7.58 (1H, d, J=8.0Hz, H-4), 7.34 (1H, d, J=8.0Hz, H-7), 7.12 (1H, d, J=2.0Hz, C-2), 7.07 (1H, t, J=7.5Hz, H-6), 6.98 (1H, t, J=7.5Hz, H-5), 4.32 (1H, t, J=5.0Hz, H-9), 4.09 (1H, t, J=8.5Hz, H-12), 3.32 (1H, m, H-15a), 3.23 (2H, m, H-15b, H-8a), 3.09 (1H, dd, J=14.5, 5.5Hz, H-8b), 1.99 (1H, m, H-14a), 1.68 (1H, m, H-14b), 1.61 (1H, m, H-13a), 1.40 (1H, m, H-13b). 13C NMR (125MHz, CD3OD) δ: 169.0 (C, C-11), 165.5 (C, C-17), 135.9 (C, C-7a), 127.3 (C, C-3a), 124.4 (CH, C-2), 120.8 (CH, C-6), 118.6 (CH, C-4), 118.2 (CH, C-5), 111.2 (CH, C-7), 109.2 (C, C-3), 58.4 (CH, C-12), 55.2 (CH, C-9), 44.6 (CH2, C-15), 27.6 (CH2, C-14), 25.8 (CH2, C-8), 21.8 (CH2, C-13).
Cyclo-(L-Pro-L-Tyr) (8): ESI-MS m/z: 261 [M+H]+; -51.2° (c 0.2 MeoH); 1H NMR (500MHz, CD3OD) δ: 7.28 (1H, s, NH-2), 7.09 (2H, d, J=7.5Hz, H-12, H-16), 6.81 (2H, d, J=7.5Hz, H-13, H-15), 5.89 (1H, s, NH-8), 4.25 (1H, dd, J=9.5, 2.0Hz, H-9), 4.12 (1H, t, J=8.0Hz, H-6), 3.67 (1H, m, H-3a), 3.61 (1H, m, H-3b), 3.52 (1H, dd, J=15.0, 4.0Hz, H-10a), 2.82 (1H, dd, J=14.5, 10.0Hz, H-10b), 2.38 (1H, m, H-5a), 2.04 (1H, m, H-4a), 1.96 (1H, m, H-5b), 1.94 (1H, m, H-4b). 13C NMR (125MHz, CD3OD) δ: 169.7 (C, C-7), 165.2 (C, C-1), 155.6 (C, C-14), 130.3 (CH, C-12, C-16), 127.0 (C, C-11), 116.1 (CH, C-13, C-15), 59.2 (CH, C-6), 56.3 (CH, C-9), 45.5 (CH2, C-3), 35.9 (CH2, C-10), 28.4 (CH2, C-5), 22.5 (CH2, C-4).