2,3-bis(nitrooxy)propyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate → 2,3-bis(nitrooxy)propyl (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate

HRID 1437591Notes

Reaction equation

HRID 1437591 reaction equation
[C:1](=[O:43])([O:14][CH2:15]/[C:16](/[C:33]1[CH:38]=[CH:37][C:36]([S:39]([CH3:42])(=[O:41])=[O:40])=[CH:35][CH:34]=1)=[C:17](/[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)\[CH2:18][O:19][Si](C(C)(C)C)(C)C)[O:2][CH2:3][CH:4]([O:10][N+:11]([O-:13])=[O:12])[CH2:5][O:6][N+:7]([O-:9])=[O:8]>CC#N.C1(C)C=CC=CC=1>[C:1](=[O:43])([O:14][CH2:15]/[C:16](/[C:33]1[CH:38]=[CH:37][C:36]([S:39]([CH3:42])(=[O:40])=[O:41])=[CH:35][CH:34]=1)=[C:17](/[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)\[CH2:18][OH:19])[O:2][CH2:3][CH:4]([O:10][N+:11]([O-:13])=[O:12])[CH2:5][O:6][N+:7]([O-:9])=[O:8]

Participants

4

Reactant 1

HCID 866234332,3-bis(nitrooxy)propyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate

Product 1

HCID 866234342,3-bis(nitrooxy)propyl (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonateYield 101.1%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6342AcetonitrileSolvent

Procedure

To a 0° C. solution of 3.73 g of 2,3-bis(nitrooxy)propyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate in 150 mL of MeCN was added 5 mL of 70% PyHF. The resultant mixture was allowed to warm to rt and stirred for an additional 4 h. The reaction mixture was diluted with 600 mL of toluene and filtered through a plug of silica gel, eluting with EtOAc. The filtrate was concentrated and the resulting residue was further purified by flash chromatography over silica gel (10-50% EtOAc/hexane) to afford 3.1 g of the title compound along with a 20% impurity. 1H NMR of major compound (500 MHz, acetone-d6): δ 7.72 (d, 2H), 7.37 (d, 2H), 7.17-7.11 (m, 5H), 5.79-5.73 (m, 1H), 5.38 (s, 2H), 5.05 (dd, 1H), 4.87 (dd, 1H), 4.68-4.65 (m, 3H), 4.49 (dd, 1H), 4.15 (t, 1H), 3.05 (s, 3H).

Workup

  1. filtrationfiltered through a plug of silica gel
  2. washeluting with EtOAc
  3. concentrationThe filtrate was concentrated
  4. customthe resulting residue was further purified by flash chromatography over silica gel (10-50% EtOAc/hexane)

Sources & evidence

ORD record
ord-7047e32487d447d8aa64fdedfb210247
Source dataset
uspto-grants-2009_11
Patent number
US07622501B2

Reaction notes

Loading…