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. Author manuscript; available in PMC: 2022 May 13.
Published in final edited form as: J Med Chem. 2021 Apr 22;64(9):5577–5592. doi: 10.1021/acs.jmedchem.0c02041

Table 1:

Summary of the Pyrrolidine Bis-Cyclic Guanidine Pharmacology at the Selected Mouse Melanocortin Receptors

ID R1 R2 R3 R4 EC50(nM)
mMC1R mMC3R mMC4R mMC5R
NDP-MSH [(Nle4, DPhe7)α-MSH] 0.09 ± 0.03 0.36 ± 0.04 0.12 ± 0.01 2.6 ± 0.6
α-MSH 0.64 ± 0.16 0.56 ± 0.06 1.6 ± 0.2 0.7 ± 0.2
Ac-His-DPhe-Arg-Trp-NH2 13.4 ± 3.9 31 ± 9 5.5 ± 0.8 4.2 ± 1
THIQ 100 ± 20 260 ± 20a 0.9 ± 0.2 0.49 ± 0.08
1 R-isobutyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl adamantan-1-yl-methyl 330 ± 110 240 ± 40 650 ± 120 (55%)
pA2= 5.5 ± 1.1
340 ± 140
2 R-isobutyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl 4-tbutyl-cyclohexyl-methyl 300 ± 90 210 ± 50 270 ± 70 (45%)
pA2 = 5.8 ± 0.1
140 ± 70
3 R-isobutyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl 4-methylpentyl 7300 ± 4400 58% @ 10 μM (B) (A) 630 ± 50
4 R-isobutyl R-cyclohexyl-methyl R-propyl adamantan-1-yl-methyl 70% @ 10 μM (B) 67% @ 10 μM (B) 51% @ 10 μM (B) 470 ± 90
5 R-isobutyl R-cyclohexyl-methyl R-propyl 4-tbutyl-cyclohexyl-methyl 500 ± 50 75% @ 10 μM (B) 65% @ 10 μM (B) 530± 50
6 R-isobutyl R-cyclohexyl-methyl R-propyl 4-methylpentyl 2300 ± 90 58% @ 10 μM (B) 6700 ± 2400 1800 ± 130
7 R-isobutyl R-cyclohexyl-methyl R-isopropyl adamantan-1-yl-methyl 570 ± 150 70% @ 10 μM (B) 50% @ 10 μM (A) 500 ± 40
8 R-isobutyl R-cyclohexyl-methyl R-isopropyl 4-tbutyl-cyclohexyl-methyl 54% @ 10 μM (B) 69% @ 10 μM (B) >100,000 560 ± 50
9 R-isobutyl R-cyclohexyl-methyl R-isopropyl 4-methylpentyl 50% @ 10 μM (B) 33% @ 10 μM (A) (B) 1850 ± 800
10 R-isobutyl R-benzyl (S,R)-1-hydroxyethyl adamantan-1-yl-methyl 41% @ 10 μM (A) 360 ± 40 58% @ 10 μM (B)
pA2 = 5.6 ± 0.2
810 ± 280
11 R-isobutyl R-benzyl (S,R)-1-hydroxyethyl 4-tbutyl-cyclohexyl-methyl 58% @ 10 μM (B) 310 ± 60 (A)
pA2 = 7.0 ± 0.7
530 ± 50
12 R-isobutyl R-benzyl (S,R)-1-hydroxyethyl 4-methylpentyl 62% @ 10 μM (B) >100,000 >100,000 77% @ 10 μM (B)
13 R-isobutyl R-benzyl R-propyl adamantan-1-yl-methyl 7000 ± 6100 74% @ 10 μM (B) 1330 ± 510 610 ± 160
14 R-isobutyl R-benzyl R-propyl 4-tbutyl-cyclohexyl-methyl 38% @ 10 μM (A) 83% @ 10 μM (B) 28% @ 10 μM (A) 480 ± 170
15 R-isobutyl R-benzyl R-propyl 4-methylpentyl >100,000 >100,000 (B) 2180 ± 625
16 R-isobutyl R-benzyl R-isopropyl adamantan-1-yl-methyl 15500 ± 14000 67% @ 10 μM (B) 8200 ± 3550 440 ± 110
17 R-isobutyl R-benzyl R-isopropyl 4-tbutyl-cyclohexyl-methyl 6800 ± 600 62% @ 10 μM (B) >100,000 560 ± 170
18 R-isobutyl R-benzyl R-isopropyl 4-methylpentyl >100,000 (A) (A) 1260 ± 130
19 R-isopropyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl adamantan-1-yl-methyl 200 ± 80 370 ± 90 49% @ 10 μM (A)
pA2 = 5.8 ± 0.1
600 ± 210
20 R-isopropyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl 4-tbutyl-cyclohexyl-methyl 300 ± 120 220 ± 30 41% @ 10 μM (A)
pA2 = 5.9 ± 0.1
150 ± 20
21 R-isopropyl R-cyclohexyl-methyl (S,R)-1-hydroxyethyl 4-methylpentyl 700 ± 80 5200 ± 1540 >100,000 740 ± 270
22 R-isopropyl R-cyclohexyl-methyl R-propyl adamantan-1-yl-methyl 550 ± 170 2800 ± 1800 45% @ 10 μM (A) 590 ± 180
23 R-isopropyl R-cyclohexyl-methyl R-propyl 4-tbutyl-cyclohexyl-methyl (B) 350 ± 20 50% @ 10 μM (A)
pA2 = 5.8 ± 0.2
540 ± 50
24 R-isopropyl R-cyclohexyl-methyl R-propyl 4-methylpentyl (B) (B) 40% @ 10 μM (A) 1040 ± 150
25 R-isopropyl R-cyclohexyl-methyl R-isopropyl adamantan-1-yl-methyl 300 ± 30 3700 ± 880 40% @ 10 μM (A) 580 ± 160
26 R-isopropyl R-cyclohexyl-methyl R-isopropyl 4-tbutyl-cyclohexyl-methyl 290 ± 20 4300 ± 3300 28% @ 10 μM (A) 510 ± 50
27 R-isopropyl R-cyclohexyl-methyl R-isopropyl 4-methylpentyl 6100 ± 4700 (B) (B) 1700 ± 520
28 R-isopropyl R-benzyl (S,R)-1-hydroxyethyl adamantan-1-yl-methyl 440 ± 140 360 ± 10 580 ± 130 (75%)
pA2 = 5.8 ± 0.1
180 ± 90
29 R-isopropyl R-benzyl (S,R)-1-hydroxyethyl 4-tbutyl-cyclohexyl-methyl 600 ± 340 420 ± 120 (A)
pA2 = 6.5 ± 0.5
490 ± 155
30 R-isopropyl R-benzyl (S,R)-1-hydroxyethyl 4-methylpentyl (B) >100,000 >100,000 40% @ 10 μM (A)
31 R-isopropyl R-benzyl R-propyl adamantan-1-yl-methyl 6700 ± 4700 2000 ± 850 1400 ± 760 6600 ± 5740
32 R-isopropyl R-benzyl R-propyl 4-tbutyl-cyclohexyl-methyl 2300 ± 1000 6200 ± 5400 27% @ 10 μM (A) 940 ± 340
33 R-isopropyl R-benzyl R-propyl 4-methylpentyl 22900 ± 10000 >100,000 41% @ 10 μM (A) 2030 ± 980
34 R-isopropyl R-benzyl R-isopropyl adamantan-1-yl-methyl 47800 ± 23100 4000 ± 1900 54% @ 10 μM (B) 660 ± 130
35 R-isopropyl R-benzyl R-isopropyl 4-tbutyl-cyclohexyl-methyl 29100 ± 20000 68% @ 10 μM (B) >100,000 600 ± 170
36 R-isopropyl R-benzyl R-isopropyl 4-methylpentyl 10220 ± 6570 >100,000 21% @ 10 μM (A) 1600 ± 460
37 R-2-butyl R-benzyl R-4-hydroxybenzyl 4-tbutyl-cyclohexyl-methyl 290 ± 20 65% @ 10 μM (B) 23% @ 10 μM (A) 380 ± 50

The compounds were screened at the selected receptor subtypes for agonist activity from 10−4 to 10−10 M and the results are tabulated as the mean EC50 values of duplicate values for at least three independent experiments. For select compounds, the 100 μM concentration resulted in cytotoxicity and was excluded from the sigmoidal dose-response fittings. For these compounds, the activity observed at 10 μM relative to maximal expression was tabulated to aide in the differentiation between partial agonists which have both a reported EC50 and percent activation and compounds that exhibited some receptor activation at 10 μM. These compounds were binned as A (10-50% receptor activation) or B (51-90% receptor activation). Follow up antagonist experiments and corresponding pA2 values, via a Schild analysis,73 were determined for the mMC4R if the compound possessed a nanomolar EC50 value (< 1 μM) at the mMC3R and produced little to no activity at the mMC4R (< 20% of maximal activity). Included as positive controls were α-MSH, the α-MSH analogue NDP-MSH, the tetrapeptide Ac-His-DPhe-Arg-Trp-NH2, and the THIQ small molecule.

a

The efficacy of THIQ was observed to be 90-95% at the mMC3R compared to the maximal response of α-MSH.