(1R,3aS,5aR,5bR,7aR,11aR,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 trifluoromethanesulfonate → methyl 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)cyclohexa-1,3-dienecarboxylate

HRID 1401037Notes

Reaction equation

HRID 1401037 reaction equation
FC(F)(F)S(O[C:7]1[C:8]([CH3:36])([CH3:35])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:34])([C@@:13]3([CH3:33])[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([NH2:32])[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)(=O)=O.CC1(C)C(C)(C)OB([C:47]2[CH2:52][CH2:51][C:50]([C:53]([O:55][CH3:56])=[O:54])=[CH:49][CH:48]=2)O1>>[NH2:32][C@:16]12[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:17]1[C@@H:18]1[C@@:13]([CH3:33])([CH2:14][CH2:15]2)[C@@:12]2([CH3:34])[C@@H:21]([C@:22]3([CH3:25])[C@@H:9]([CH2:10][CH2:11]2)[C:8]([CH3:35])([CH3:36])[C:7]([C:47]2[CH2:52][CH2:51][C:50]([C:53]([O:55][CH3:56])=[O:54])=[CH:49][CH:48]=2)=[CH:24][CH2:23]3)[CH2:20][CH2:19]1

Participants

3

Reactant 2

HCID 71698571(1R,3aS,5aR,5bR,7aR,11aR,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 trifluoromethanesulfonateHCID 86692396Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexa-1,3-dienecarboxylate

Product 1

HCID 86692397methyl 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)cyclohexa-1,3-dienecarboxylateYield 60.8%

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-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 methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexa-1,3-dienecarboxylate as the reactants. (60.8% yield). MS: m/e 529.5 (M−16)+, 2.816 min (method 8). 1H NMR (400 MHz, CHLOROFORM-d) δ 6.99 (d, J=5.8 Hz, 1H), 5.78 (d, J=5.8 Hz, 1H), 5.27 (dd, J=6.0, 1.8 Hz, 1H), 4.70 (d, J=2.0 Hz, 1H), 4.57 (d, J=1.3 Hz, 1H), 3.72 (s, 3H), 2.52 (td, J=10.8, 5.3 Hz, 1H), 2.48-2.39 (m, 1H), 2.36-2.29 (m, 1H), 2.09-1.95 (m, 2H), 1.76-1.20 (m, 22H), 1.66 (s, 3H), 1.05 (s, 3H), 0.98 (s, 3H), 0.94 (s, 6H), 0.86 (s, 3H).

Workup

  1. customdescribed in step 1 for the preparation of Example 1
  2. customm/e 529.5 (M−16)+, 2.816 min (method 8)

Sources & evidence

ORD record
ord-fc42aa2fd4d04cc19bb28c9f77f5a312
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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