2-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-[[3-(1,1-dioxo-1,4-thiazinan-4-yl)propylamino]methyl]-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]spiro[3.3]hept-2-ene-6,6-dicarboxylic acid → ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-(1,1-dioxidothiomorpholino)ethyl)amino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-methylcyclohexa-1,3-dienecarboxylate

HRID 1401025Notes

Reaction equation

[O:1]=[S:2]1(=[O:55])[CH2:7][CH2:6][N:5]([CH2:8][CH2:9]CNC[C@]23CC[C@@H](C(C)=C)[C@@H]2[C@@H]2[C@@](C)(CC3)[C@@]3(C)[C@@H]([C@]4(C)[C@@H](CC3)C(C)(C)C(C3CC5(CC(C(O)=O)(C(O)=O)C5)C=3)=CC4)CC2)[CH2:4][CH2:3]1.[NH2:56][C@:57]12[CH2:94][CH2:93][C@@H:92]([C:95]([CH3:97])=[CH2:96])[C@@H:58]1[C@@H:59]1[C@@:72]([CH3:75])([CH2:73][CH2:74]2)[C@@:71]2([CH3:76])[C@@H:62]([C@:63]3([CH3:91])[C@@H:68]([CH2:69][CH2:70]2)[C:67]([CH3:78])([CH3:77])[C:66]([C:79]2[CH2:84][CH2:83][C:82]([C:85]([O:87][CH2:88][CH3:89])=[O:86])=[C:81]([CH3:90])[CH:80]=2)=[CH:65][CH2:64]3)[CH2:61][CH2:60]1>>[O:1]=[S:2]1(=[O:55])[CH2:7][CH2:6][N:5]([CH2:8][CH2:9][NH:56][C@:57]23[CH2:94][CH2:93][C@@H:92]([C:95]([CH3:97])=[CH2:96])[C@@H:58]2[C@@H:59]2[C@@:72]([CH3:75])([CH2:73][CH2:74]3)[C@@:71]3([CH3:76])[C@@H:62]([C@:63]4([CH3:91])[C@@H:68]([CH2:69][CH2:70]3)[C:67]([CH3:77])([CH3:78])[C:66]([C:79]3[CH2:84][CH2:83][C:82]([C:85]([O:87][CH2:88][CH3:89])=[O:86])=[C:81]([CH3:90])[CH:80]=3)=[CH:65][CH2:64]4)[CH2:61][CH2:60]2)[CH2:4][CH2:3]1

Participants

Reactant 2

HCID 865754482-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-[[3-(1,1-dioxo-1,4-thiazinan-4-yl)propylamino]methyl]-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]spiro[3.3]hept-2-ene-6,6-dicarboxylic acid

HCID 86692381ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-methylcyclohexa-1,3-dienecarboxylate

Product 1

HCID 86692382ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-(1,1-dioxidothiomorpholino)ethyl)amino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-methylcyclohexa-1,3-dienecarboxylate

Procedure

The title compound was prepared following the method described above in Step 2 for the preparation of 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(((3-(1,1-dioxidothiomorpholino)propyl)amino)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)spiro[3.3]hept-5-ene-2,2-dicarboxylic acid (example A14), using ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-methylcyclohexa-1,3-dienecarboxylate as the reactant. (quantitative yield). MS: m/e 735.8 (M+H)+, 3.41 min (method 3). 1H NMR (400 MHz, CHLOROFORM-d) δ 5.65 (s, 1H), 5.28 (dd, J=6.0, 1.5 Hz, 1H), 4.71 (s, 1H), 4.59 (s, 1H), 4.19 (q, J=7.1 Hz, 2H), 3.15-2.97 (m, 8H), 2.73-2.51 (m, 4H), 2.50-2.38 (m, 3H), 2.22 (q, J=8.3 Hz, 2H), 2.15 (s, 3H), 2.06-1.18 (m, 25H), 1.11-1.04 (m, 6H), 1.00 (s, 3H), 0.98-0.95 (m, 6H), 0.88 (s, 3H).

Workup

customm/e 735.8 (M+H)+, 3.41 min (method 3)

Sources & evidence

ORD record: ord-c8117718699942088ac77cffe9e59213
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08906889B2

Reaction notes

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