7,12-Dimethylbenz(a)anthracene → HCID 18463948, compound

HRID 2231094Notes

Reaction equation

HRID 2231094 reaction equation
C([O:4][C:5]1[C:43]([Cl:44])=[CH:42][C:8]([C:9]([NH:11][CH:12]2[CH2:18][CH2:17][CH2:16][N:15]([S:19]([CH3:22])(=[O:21])=[O:20])[N:14]([CH2:23][C:24](=[O:40])[NH:25][CH:26]3[CH2:30][C:29](=[O:31])[O:28][CH:27]3[O:32][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:13]2=[O:41])=[O:10])=[CH:7][C:6]=1[Cl:45])C=C.CC1C2C(=CC=CC=2)C(C)=C2C=1C=CC1C2=CC=CC=1>ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:33]([O:32][CH:27]1[CH:26]([NH:25][C:24]([CH2:23][N:14]2[C:13](=[O:41])[CH:12]([NH:11][C:9](=[O:10])[C:8]3[CH:7]=[C:6]([Cl:45])[C:5]([OH:4])=[C:43]([Cl:44])[CH:42]=3)[CH2:18][CH2:17][CH2:16][N:15]2[S:19]([CH3:22])(=[O:20])=[O:21])=[O:40])[CH2:30][C:29](=[O:31])[O:28]1)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

5

Reactant 2

HCID 60017,12-Dimethylbenz(a)anthraceneHCID 18463929HCID 18463929, compound

Product 1

HCID 18463948HCID 18463948, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent2×

Procedure

4-Allyloxy-N-{2-[(2-benzyloxy-5-oxo-tetrahydro-furan-3-ylcarbamoyl)-methyl]-1-methanesulfonyl-3-oxo-[1,2]diazepan-4-yl}-3,5-dichloro-benzamide (26a) (178 mg, 0.26 mmol) in dichloromethane (6 mL) was treated with DMBA (45 mg, 0.29 mmol) and Pd(PPh3)4 (20 mg, 0.017 mmol) at room temperature for 16 hours. The mixture was diluted with dichloromethane (40 mL), washed with water three times. The organic layer was dried over anhydrous Na2SO4, filtered and evaporated to give a pale yellow solid, that was purified by flash chromatography using dichloromethane/methanol (99.2/0.8 to 97.5/2.5) to afford 78 mg (47% yield) of syn diastereomer (higher Rf) of the title compound and 59 mg (35% yield) of anti diastereomer (lower Rf). 1H-NMR (500 MHz, CDCl3) for the syn diastereomer: δ 1.60-1.70 (m, 1H), 1.88-1.91 (m, 1H), 2.22-2.32 (m, 2H), 2.48-2.58 (m, 1H), 2.84-2.90 (m, 1H), 3.00 (s, 3H), 3.27-3.40 (m, 1H), 4.05-4.18 (m, 2H), 4.22-4.35 (m, 1H), 4.55-4.80 (m, 2H), 4.86-4.89 (d, 1H), 5.10-5.15 (m, 1H), 5.59-5.61 (d, 1H), 6.75-6.77 (d, 1H), 7.05-7.07 (d, 1H), 7.25-7.37 (m, SH), 7.70 (s, 2H); and for the anti diastereomer: δ 1.60-1.80 (m, 1H), 1.85-1.95 (m, 1H), 2.20-2.39 (m, 2H), 2.39-2.50 (m, 1H), 3.00-3.10 (m, 1H), 3.12 (s, 3H), 3.28-3.42 (m, 1H), 4.05-4.15 (m, 2H), 4.28-4.47 (m, 2H), 4.56-4.62 (m, 1H), 4.77-4.83 (d, 1H), 5.10-5.20 (m, 1H), 5.43 (s, 1H), 6.93-6.94 (d, 1H), 7.09-7.11 (d, 1H), 7.25-7.39(m, SH), 7.80 (s, 2H). Analytical HPLC: 11.13 and 11.36 min. LC-MS (ES+) for the mixture of diastereomers: m/e=643, 645 (M+H+).

Workup

  1. washwashed with water three times
  2. dry with materialThe organic layer was dried over anhydrous Na2SO4
  3. filtrationfiltered
  4. customevaporated
  5. customto give a pale yellow solid, that
  6. customwas purified by flash chromatography

Sources & evidence

ORD record
ord-db63e1c6ec4e4b91bdfdcfee44922751
Source dataset
uspto-grants-2002_07
Patent number
US06426413B1

Reaction notes

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