HCID 66910183, compound → HCID 66910132, compound

HRID 910604Notes

Reaction equation

HRID 910604 reaction equation
[CH3:1][Si:2]([CH3:36])([C:32]([CH3:35])([CH3:34])[CH3:33])[O:3][C@H:4]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[CH:6]([C@@H:7]([OH:31])[CH2:8][C@@H:9]3[C@@H:18]2[CH2:17][CH2:16][C@@:14]2([CH3:15])[C@H:10]3[CH2:11][CH2:12][C@@H:13]2[O:23][Si:24]([CH3:30])([CH3:29])[C:25]([CH3:28])([CH3:27])[CH3:26])[CH2:5]1.[CH3:37][Si:38]([CH3:72])([C:68]([CH3:71])([CH3:70])[CH3:69])[O:39][C@@H:40]1[CH2:57][CH2:56][C@@:55]2([CH3:58])[CH:42]([C@@H:43]([OH:67])[CH2:44][C@@H:45]3[C@@H:54]2[CH2:53][CH2:52][C@@:50]2([CH3:51])[C@H:46]3[CH2:47][CH2:48][C@@H:49]2[O:59][Si:60]([CH3:66])([CH3:65])[C:61]([CH3:64])([CH3:63])[CH3:62])[CH2:41]1>C(Cl)Cl.CCC[N+](CCC)(CCC)CCC.[O-][Ru](=O)(=O)=O>[CH3:36][Si:2]([CH3:1])([C:32]([CH3:35])([CH3:34])[CH3:33])[O:3][C@H:4]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[CH:6]([C:7](=[O:31])[CH2:8][C@@H:9]3[C@@H:18]2[CH2:17][CH2:16][C@@:14]2([CH3:15])[C@H:10]3[CH2:11][CH2:12][C@@H:13]2[O:23][Si:24]([CH3:29])([CH3:30])[C:25]([CH3:26])([CH3:27])[CH3:28])[CH2:5]1.[CH3:72][Si:38]([CH3:37])([C:68]([CH3:71])([CH3:70])[CH3:69])[O:39][C@@H:40]1[CH2:57][CH2:56][C@@:55]2([CH3:58])[CH:42]([C:43](=[O:67])[CH2:44][C@@H:45]3[C@@H:54]2[CH2:53][CH2:52][C@@:50]2([CH3:51])[C@H:46]3[CH2:47][CH2:48][C@@H:49]2[O:59][Si:60]([CH3:65])([CH3:66])[C:61]([CH3:62])([CH3:63])[CH3:64])[CH2:41]1

Participants

6

Reactant 2

HCID 66910183HCID 66910183, compoundHCID 66910196HCID 66910196, compound

Product 2

HCID 66910124HCID 66910124, compoundHCID 66910132HCID 66910132, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3β,17β-di(dimethyltert-butylsilyloxy)androstane-6α-ol and 3α,17β-di(dimethyltert-butylsilyloxy)androstane-6α-ol (90/10 mixture, 6.30 g) in CH2Cl2 (60 mL) under N2, NMNO (4.07 g), TPAP (0.412 g) and 4 Å molecular sieves (3.50 g) were added. The mixture was stirred for 2 h and then SiO2 was added. The mixture was purified by flash chromatography (SiO2, n-hexane/Et2O 50/50) to give 3β,17β-di(dimethyltert-butylsilyloxy)-androstane-6-one and 3α,17β-di(dimethyltert-butylsilyloxy)androstane-6-one (90/10 mixture, 6.30 g, 100%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 3.68 (m, 1H), 3.67-3.57 (m, 1H), 2.38-2.30 (m, 1H), 2.20-2.12 (m, 1H), 1.99-1.05 (m, 18H), 0.90 (s, 9H), 0.88 (s, 9H), 0.75 (s, 3H), 0.74 (s, 3H), 0.07-0.03 (s, 12H).

Workup

  1. additionSiO2 was added
  2. customThe mixture was purified by flash chromatography (SiO2, n-hexane/Et2O 50/50)

Sources & evidence

ORD record
ord-d43932d137e840c0b81656bf70a201de
Source dataset
uspto-grants-2011_09
Patent number
US08022203B2

Reaction notes

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