HCID 57941616, compound → HCID 57941619, compound

HRID 1437585Notes

Reaction equation

[C:1](=[O:45])([O:16][CH2:17]/[C:18](/[C:35]1[CH:40]=[CH:39][C:38]([S:41]([CH3:44])(=[O:43])=[O:42])=[CH:37][CH:36]=1)=[C:19](/[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)\[CH2:20][O:21][Si](C(C)(C)C)(C)C)[O:2][CH2:3][CH2:4][CH2:5][CH:6]([O:12][N+:13]([O-:15])=[O:14])[CH2:7][O:8][N+:9]([O-:11])=[O:10]>C(#N)C.C1(C)C=CC=CC=1>[C:1](=[O:45])([O:16][CH2:17]/[C:18](/[C:35]1[CH:40]=[CH:39][C:38]([S:41]([CH3:44])(=[O:42])=[O:43])=[CH:37][CH:36]=1)=[C:19](/[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)\[CH2:20][OH:21])[O:2][CH2:3][CH2:4][CH2:5][CH:6]([O:12][N+:13]([O-:15])=[O:14])[CH2:7][O:8][N+:9]([O-:11])=[O:10]

Participants

Conditions

Temperature: 25 °C

Procedure

To a solution of 18 ml of phosgene (1.93 M /toluene) at −78° C. under N2, was added 3 g of 3,4-bis(nitrooxy)butyl alcohol. The resulted mixture was stirred at 25° C. for 24 h. Distillation of excess phosgene was done under low vacuum at 50° C. to afford 4.2 g of the desired compound as an orange oil. The crude compound was used directly in the next reaction. To a solution of 3.5 g of (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-ol, 1.0 g of DMAP and 1.8 mL of Hünig's base in 40 mL of CH2Cl2 at −78° C. was added 3.3 g of 4,5-bis(nitrooxy)pentyl chloridocarbonate. The reaction mixture was stirred for 2 h at 25° C. and then filtered through a pad of silica gel, washed with EtOAc and evaporated. Purification by flash chromatography afforded 5.4 g of the titled compound as a yellowish oil. The compound was used directly in the next step. To a solution of 5.4 g of 4,5-bis(nitrooxy)pentyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate in 50 mL of acetonitrile was added 2.5 mL of HF.pyr and the mixture was stirred at 25° C. for 1.5 h. The reaction mixture was diluted with 200 mL of toluene, loaded on silica gel and washed with EtOAc. Purification by flash chromatography afforded 4.6 g of the titled compound as a colorless oil. 1H NMR (acetone-d6, 500 MHz): δ 7.69 (d, 2H), 7.34 (d, 2H), 7.14-7.08 (m, 5H), 5.30 (s, 2H), 5.01 (dd, 1H), 4.73 (dd, 1H), 4.64 (d, 2H), 4.17-4.11 (m, 3H), 4.04 (q, 4H), 3.03 (s, 3H), 1.91-1.81 (m, 4H).

Workup

washwashed with EtOAc
customPurification by flash chromatography

Sources & evidence

ORD record: ord-994d6f0d40a4469aa41aea43b2975400
Source dataset: uspto-grants-2009_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07622501B2

Reaction notes

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