4-(Methanesulfonyl)piperidine → ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(4-(methylsulfonyl)piperidin-1-yl)ethyl)amino)-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)bicyclo[3.1.0]hex-2-ene-6-carboxylate

HRID 1401034Notes

Reaction equation

HRID 1401034 reaction equation
N1([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(=O)CC4)CC2)CC1.[CH3:34][S:35]([CH:38]1[CH2:43][CH2:42][NH:41][CH2:40][CH2:39]1)(=[O:37])=[O:36].[N:44]1([C@:47]23[CH2:83][CH2:82][C@@H:81]([C:84]([CH3:86])=[CH2:85])[C@@H:48]2[C@@H:49]2[C@@:62]([CH3:65])([CH2:63][CH2:64]3)[C@@:61]3([CH3:66])[C@@H:52]([C@:53]4([CH3:80])[C@@H:58]([CH2:59][CH2:60]3)[C:57]([CH3:68])([CH3:67])[C:56]([C:69]3[CH2:74][CH:73]5[CH:71]([CH:72]5[C:75]([O:77][CH2:78][CH3:79])=[O:76])[CH:70]=3)=[CH:55][CH2:54]4)[CH2:51][CH2:50]2)[CH2:46][CH2:45]1>>[CH3:65][C@:62]12[C@@:61]3([CH3:66])[C@@H:52]([C@:53]4([CH3:80])[C@@H:58]([CH2:59][CH2:60]3)[C:57]([CH3:67])([CH3:68])[C:56]([C:69]3[CH2:74][CH:73]5[CH:71]([CH:72]5[C:75]([O:77][CH2:78][CH3:79])=[O:76])[CH:70]=3)=[CH:55][CH2:54]4)[CH2:51][CH2:50][C@@H:49]1[C@H:48]1[C@H:81]([C:84]([CH3:86])=[CH2:85])[CH2:82][CH2:83][C@:47]1([NH:44][CH2:45][CH2:46][N:41]1[CH2:42][CH2:43][CH:38]([S:35]([CH3:34])(=[O:37])=[O:36])[CH2:39][CH2:40]1)[CH2:64][CH2:63]2

Participants

4

Reactant 3

HCID 222750384-(Methanesulfonyl)piperidineHCID 71698573(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-oneHCID 86692393ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-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)bicyclo[3.1.0]hex-2-ene-6-carboxylate

Product 1

HCID 86692394ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(4-(methylsulfonyl)piperidin-1-yl)ethyl)amino)-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)bicyclo[3.1.0]hex-2-ene-6-carboxylateYield 33.2%

Procedure

The title compound was prepared following the method describe on step 1 for the preparation of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one using 4-(methylsulfonyl)piperidine and ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-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)bicyclo[3.1.0]hex-2-ene-6-carboxylate as the reactants. The product was obtained as a mixture of diastereomers in 33.2% yield. MS: m/e 749.6 (M+H)+, 2.794 min (method 8). 1H NMR (400 MHz, CHLOROFORM-d) δ 5.84-5.75 (m, 1H), 5.49-5.38 (m, 1H), 4.69 (br. s., 1H), 4.59 (br. s., 1H), 4.19-4.04 (m, 2H), 3.12 (dd, J=15.6, 12.8 Hz, 1H), 2.98-2.74 (m, 7H), 2.68-2.51 (m, 5H), 2.45 (d, J=7.5 Hz, 4H), 2.22-2.10 (m, 3H), 2.09-1.74 (m, 8H), 1.69 (s, 3H), 1.65-1.30 (m, 12H), 1.26 (m, 6H), 1.06 (br. s., 5.5H), 1.02 (s, 3H), 0.98-0.92 (m, 4.5H), 0.85-0.78 (m, 3H).

Workup

  1. customThe product was obtained as a mixture of diastereomers in 33.2% yield
  2. customm/e 749.6 (M+H)+, 2.794 min (method 8)

Sources & evidence

ORD record
ord-440540b22a954ff4bef44cfda9cbda92
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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