(1R,3aS,5aR,5bR,7aR,11aR,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 trifluoromethanesulfonate → ethyl 5-((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-methyl-4H-1,3-dioxine-2-carboxylate

HRID 1401027Notes

Reaction equation

HRID 1401027 reaction equation
FC(F)(F)S(O[C:7]1[C:8]([CH3:46])([CH3:45])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:44])([C@@:13]3([CH3:43])[C@H:18]([CH2:19][CH2:20]1)[C@H:17]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:16]1([NH:32][CH2:33][CH2:34][N:35]1[CH2:40][CH2:39][S:38](=[O:42])(=[O:41])[CH2:37][CH2:36]1)[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)(=O)=O.[CH3:49][C:50]1([C:65]([O:67][CH2:68][CH3:69])=[O:66])[O:55][CH2:54][C:53](B2OC(C)(C)C(C)(C)O2)=[CH:52][O:51]1>>[O:42]=[S:38]1(=[O:41])[CH2:39][CH2:40][N:35]([CH2:34][CH2:33][NH:32][C@:16]23[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:17]2[C@@H:18]2[C@@:13]([CH3:43])([CH2:14][CH2:15]3)[C@@:12]3([CH3:44])[C@@H:21]([C@:22]4([CH3:25])[C@@H:9]([CH2:10][CH2:11]3)[C:8]([CH3:45])([CH3:46])[C:7]([C:53]3[CH2:54][O:55][C:50]([CH3:49])([C:65]([O:67][CH2:68][CH3:69])=[O:66])[O:51][CH:52]=3)=[CH:24][CH2:23]4)[CH2:20][CH2:19]2)[CH2:36][CH2:37]1

Participants

3

Reactant 2

HCID 71698666(1R,3aS,5aR,5bR,7aR,11aR,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 trifluoromethanesulfonateHCID 86692387ethyl 2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H-1,3-dioxine-2-carboxylate

Product 1

HCID 86692386ethyl 5-((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-methyl-4H-1,3-dioxine-2-carboxylateYield 13.3%

Procedure

The title compound was prepared following the method described in step 1 for the preparation of Example 1, using (1R,3aS,5aR,5bR,7aR,11aR,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 trifluoromethanesulfonate and ethyl 2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H-1,3-dioxine-2-carboxylate as the reactants. The product was isolated as a mixture of diasteromers in 13.3% yield. MS: m/e 741.55 (M+H)+, 2.72 min (method 8). 1H NMR (400 MHz, CHLOROFORM-d) δ 6.35-6.30 (m, 1H), 5.36 (d, J=5.5 Hz, 1H), 4.73 (s, 1H), 4.60 (s, 1H), 4.42 (ddd, J=15.4, 7.6, 1.4 Hz, 1H), 4.33-4.21 (m, 2H), 4.20-4.12 (m, 1H), 3.14-3.00 (m, 11H), 2.80-2.47 (m, 2H), 2.12-1.73 (m, 2H), 1.69 (s, 3H), 1.62 (s, 3H), 1.55-1.19 (m, 11H), 1.10-1.02 (m, 12H), 1.00-0.94 (m, 6H), 0.92-0.87 (m, 3H), 0.86-0.78 (m, 6H).

Workup

  1. customdescribed in step 1 for the preparation of Example 1
  2. customThe product was isolated as a mixture of diasteromers in 13.3% yield
  3. customm/e 741.55 (M+H)+, 2.72 min (method 8)

Sources & evidence

ORD record
ord-6bec899ec5f8499391087d85f08deedd
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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