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. Author manuscript; available in PMC: 2018 Nov 22.
Published in final edited form as: J Nat Prod. 2017 Oct 31;80(11):2969–2986. doi: 10.1021/acs.jnatprod.7b00551

Table 3.

NMR Spectroscopic Data for Grassystatin F (3) at 600 MHz (1H), 150 MHz (13C) in DMSO-d6

C/H no. δCa, type δH (J in Hz) 1H-1H COSY HMBCb ROESY
Pro 1 172.5, C
2 59.2, CH 4.29, t (7.8) H-3a, H-3b 1, 3, 4 H-3a, H-3b, H-4
3a 28.5, CH2 2.21, m H-2, H-3b, H-4 1, 4, 5 H-2, H-3b, H-4
3b 1.67, m H-2, H-3a 1, 2, 4 H-3a
4 25.1, CH2 1.75, m (2H) H-5a, H-5b H-3a, H-5b
5a 46.5, CH2 3.36, m H-4, H-5b 2, 3, 4 H-5b, H-8
5b 3.22, m H-4, H-5a 3, 4 H-4
O-Me 6 51.8, CH3 3.63, s 1
N-Me-Phe 7 168.3, C
8 55.1, CH 5.54, dd (10.1, 5.6) H-9a, H-9b 7, 9, 10, 16, 17 H-5a, H-9a, H-9b
9a 34.1, CH2 2.99, dd (−14.0, 5.6) H-8, H-9b 7, 8, 10, 11/15 H-9, H-9b
9b 2.82, dd (−14.0, 10.0) H-8, H-9a 7, 8, 10, 11/15 H-9a
10 137.8, C
11/15 129.5, CH 7.21, m H-12/14 9, 10, 12/14, 13, 11/15
12/14 127.9, CH 7.20, m H-11/15, H-13 10, 12/14, 13, 11/15 H-8, H-9a, H-9b, H3-16, H3-19
13 126.4, CH 7.16, m H-12/14 11/15
16 29.7, CH3 2.91, s 8, 17 H-8, H-12/14, H3-19
Ala 17 172.3, C
18 44.3, CH 4.53, qd (7.0, 7.1) H3-19, NH 17, 19, 20 H3-16, H3-19, NH (Ala)
19 16.3, CH3 0.71, d (7.0) H-18 17, 18 H-18, NH (Ala)
NH 8.11, d (7.1) H-18, H3-19c 18, 19, 20 H-18, H3-19, H-21, NH (Ile)
Ile 20 170.90, C
21 56.1, CH 4.18, dd (9.4, 7.0) H-22, NH 20, 22, 23, 24 H-22, H3-23, H-24a, H-24b,NH (Ile), NH (Ala)
22 37.1, CH 1.62, m H-21, H3-23 H-21, H3-23, H-24a, H-24b, NH (Ile), NH (Ala)
23 15.1, CH3 0.76, m H-22 21, 22, 24 H-22, H-24a, H-24b
24a 24.1, CH2 1.36, m H-24b, H3-25 H-24b
24b 1.01, m H-22, H-24a, H3-25 22, 23, 25 H-24a
25 11.3, CH3 0.77, m H-24a, H-24b 22, 24 H-21, NH (Ile), NH (Ala)
NH 7.76, d (9.4) H-21 21, 26 H-21, H-22, H-24b, H-27a, H-27b, NH (Ala)
Sta 26 170.97, C
27a 40.1, CH2 2.17, dd (−14, 9.0) H-27b, H-28 26, 28, 29 H-28, H-29, NH (Ile)
27b 2.11, dd (−14, 3.7) H-27a, H-28 26, 28 H-28, H-29, H-36b, NH (Ile)
28 69.4, CH 3.75, m H-27a, H-27b H-27a, H-27b, H-30b, H-43, NH (Ile)
29 50.7, CH 3.80, m H-30a, H-30b, NH H-27a, H-27b, H-30b, H3-45, NH (Sta), NH (Ile)
30a 39.6, CH2 1.35, m H-29, H-30b, H-31 29, 31, 32, 33 H-30b
30b 1.18, m H-29, H-30a 29, 31, 32, 33 H-28, H-30a
31 24.1, CH 1.65, m H-30a, H3-32, H3-33 H3-32, H3-33,
32 23.5, CH3 0.87, d (6.2) H-31 30, 31, 33 H-30a, H-31, H-41
33 21.5, CH3 0.86, d (6.2) H-31 30, 31, 32 H-42a
OH 4.74, br
NH 7.07, d (9.0) H-29 34 H-35
N-Me-Gln 34 169.8, C
35 55.5, CH 4.88, dd (9.5, 6.0) H-36a, H-36b 34, 36, 37, 39, 40 H-36a, H-36b, H-37, NH (Sta)
36a 24.0, CH2 1.96, m H-35, H-36b 37, 38 H-36b
36b 1.80, m H-35, H-36a H-36a
37 31.2, CH2 1.94, m (2H) H-36a, H-36b 35, 36, 38 H-35
38 173.8, C
39 30.3, CH3 2.90, s 35, 40 H-36b, H-37, H-41, H-42b
NH2
Leu 40 172.6, C
41 47.3, CH 4.70, m H-42a, H-42b, NH 40, 42 H3-33, H3-39, H-42b, NH (Leu)
42a 40.2, CH2 1.48, m H-41, H-42b 40, 41, 43, 44, 45 H-42b
42b 1.33, m H-41, H-42a 43, 44, 45 H-42a
43 24.3, CH 1.44, m H3-44, H3-45 H3-44
44 23.4, CH3 0.83, d (6.6) H-43 42, 43, 45 H-30b, H-42b, H-43
45 21.7, CH3 0.79, d (6.6) H-43 42, 43, 44 H-29, H-30b, H-43
NH 8.24, d (8.0) H-41 41, 46 H-41, H-42a, H-47
Lactic acid 46 169.9, C
47 69.3, CH 4.98,q (6.7) H-48 48, 49 H3-48, NH (Leu)
48 17.7, CH3 1.31,d (6.7) H-47 46, 47 H-47, NH (Leu)
N,N-diMe-Phe 49 170.2, C
50 67.9, CH 3.49, t (7.6) H-51a, H-51b 49, 51, 52, 58/59 H-51a, H-51b, H3-58/59
51a 34.8, CH2 2.95, dd (−14.0, 6.7) H-50, H-51b 49, 50, 52, 53/57 H-50, H3-58/59
51b 2.85, dd (−14.0, 6.7) H-50, H-51a 49, 50, 52, 53/57 H-50, H3-58/59
52 138.7, C
53/57 129.1, CH 7.23, m 51, 55, 53/57 H-50, H-51a, H-51b
54/56 128.2, CH 7.25, m H-55 52, 54/56
55 126.2, CH 7.18, m H-54/56 53/57 H-37
58/59 41.2, CH3 2.29, s 49, 50, 58/59 H3-48, H-50, H-51a, H-51b
a

Multiplicity derived from HSQC spectra.

b

Protons showing long-range correlation with indicated carbon.

c

These couplings were only observed in the TOCSY spectrum.