2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 117974136, compound

HRID 1776094Notes

Reaction equation

HRID 1776094 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][CH2:15][CH2:16][C@H:17]([CH2:36][CH2:37][S:38][CH3:39])[C@@H:18]([O:31][CH2:32][CH:33]([CH3:35])[CH3:34])[C@@H:19]([O:21]CC1C=CC(OC)=CC=1)[CH3:20])[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N.[OH-].[Na+]>C(Cl)Cl.O>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][CH2:15][CH2:16][C@H:17]([CH2:36][CH2:37][S:38][CH3:39])[C@@H:18]([O:31][CH2:32][CH:33]([CH3:34])[CH3:35])[C@@H:19]([OH:21])[CH3:20])[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:2])([CH3:4])[CH3:3]

Participants

6

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinone2×HCID 14798Sodium HydroxideHCID 117974140HCID 117974140, compound

Product 1

HCID 117974136HCID 117974136, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of (2S,6R,7R,8S)-methyl 2-((tert-butoxycarbonyl)amino)-7-isobutoxy-8-((4-methoxybenzyl)oxy)-6-(2-(methylthio)ethyl)nonanoate (536 mg, 0.941 mmol) and 0.85 mL H2O in CH2Cl2 (9.4 mL) at 0° C. (icewater bath) was added DDQ (214 mg, 0.941 mmol). The resulting dark mixture was stirred at 0° C. for 3 h, then another portion of DDQ (41 mg, 0.180 mmol) were added and the reaction was stirred for 1 h. The reaction was quenched with sodium hydroxide (NaOH; 1.3 ml of 1M aqueous, 1.3 mmol) and stirred for 10 min. The reaction was then diluted with H2O (20 mL) and extracted with CH2Cl2 (3×20 mL). The combined organic extracts were dried over Na2SO4, filtered, and concentrated to provide a red oil which was purified by column chromatography on SiO2 (5→35% acetone/hexanes gradient) to furnish the title product as a clear, colorless oil (353 mg, 83%): 1H NMR (400 MHz, CDCl3) δ 5.02 (d, J=8.0 Hz, 1H), 4.31 (d, J=5.2 Hz, 1H), 3.95-3.83 (m, 1H), 3.74 (d, J=1.6 Hz, 3H), 3.36 (dd, J=8.5, 6.3 Hz, 1H), 3.22 (dd, J=8.5, 6.6 Hz, 1H), 3.05 (dd, J=5.6, 3.9 Hz, 1H), 2.58 (ddd, J=14.0, 8.7, 5.3 Hz, 1H), 2.47 (ddd, J=12.8, 8.3, 7.4 Hz, 1H), 2.10 (s, 3H), 1.96-1.68 (m, 4H), 1.68-1.49 (m, 3H), 1.45 (s, 9H), 1.39 (s, 4H), 1.21 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.9 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 173.36, 155.36, 84.83, 79.93, 79.24, 68.10, 53.20, 52.27, 38.01, 33.20, 33.05, 32.76, 30.90, 29.21, 28.83, 28.33, 22.83, 19.52, 19.46, 19.11, 15.43; ESIMS m/z 450.4 ([M+H]+), 472.4 ([M+Na]+).

Workup

  1. stirringthe reaction was stirred for 1 h
  2. stirringstirred for 10 min
  3. extractionextracted with CH2Cl2 (3×20 mL)
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto provide a red oil which
  8. customwas purified by column chromatography on SiO2 (5→35% acetone/hexanes gradient)

Sources & evidence

ORD record
ord-a541db01818a40ee84020aec2d0338b8
Source dataset
uspto-grants-2016_02
Patent number
US09265253B2

Reaction notes

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