Triethylamine → 4(RS)-t-butyldimethylsilyloxy-2-(5-carboxypentylthio)-2-cyclopentenone 5,6-dihydrophenanthridinamide

HRID 358373Notes

Reaction equation

HRID 358373 reaction equation
[Si:1]([O:8][CH:9]1[CH2:13][C:12](=[O:14])[C:11]([S:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][C:21]([OH:23])=[O:22])=[CH:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].ClC(OCC(C)C)=O.C([N:34](CC)CC)C.[CH:39]1[C:52]2C3[C:46](=[CH:47][CH:48]=CC=3)[CH2:45][NH:44][C:43]=2C=C[CH:40]=1>ClCCl.C(OCC)(=O)C>[C:20]1([C:21]([NH2:34])=[O:23])[C:19]2[C:18]3[C:46](=[CH:47][CH:48]=[CH:16][CH:17]=3)[CH2:45][NH:44][C:43]=2[CH:52]=[CH:39][CH:40]=1.[Si:1]([O:8][CH:9]1[CH2:13][C:12](=[O:14])[C:11]([S:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][C:21]([OH:23])=[O:22])=[CH:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 62365Isobutyl chloroformateHCID 2199665,6-DihydrophenanthridineHCID 204488094(RS)-t-butyldimethylsilyloxy-2-(5-carboxypentylthio)-2-cyclopentenone

Product 1

HCID 204488484(RS)-t-butyldimethylsilyloxy-2-(5-carboxypentylthio)-2-cyclopentenone 5,6-dihydrophenanthridinamideYield 172.3%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-40 °C

Procedure

2.12 g (5.92 mmoles) of 4(RS)-t-butyldimethylsilyloxy-2-(5-carboxypentylthio)-2-cyclopentenone was dissolved in 30 ml of dichloromethane, and the solution was cooled to -40° C. To the solution were added 970 mg (920 microliters; 7.10 mmols) of isobutyl chloroformate and 896 mg (1.24 ml, 8.88 mmoles) of triethylamine were added, and the mixture was stirred at -40° C. for 30 minutes. Then, 10 ml of a dichloromethane solution of 1.29 g (7.10 mmoles) of 5,6-dihydrophenanthridine was added to the resulting mixture. The temperature was gradually raised to room temperature over 20 hours. After the reaction, ethyl acetate was added to the reaction mixture to perform extraction. The extract was washed with dilute hydrochloric acid, an aqueous solution of sodium bicarbonate and then an aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and concentrated. The resulting crude product was chromatographed on a silica gel column using hexane/ethyl acetate (4/1) as an eluent to give 2.657 g (5.1 mmoles; yield 86%) of 4(RS)-t-butyldimethylsilyloxy-2-(5-carboxypentylthio)-2-cyclopentenone 5,6-dihydrophenanthridinamide.

Workup

  1. additionwere added
  2. temperatureThe temperature was gradually raised to room temperature over 20 hours
  3. additionwas added to the reaction mixture
  4. extractionextraction
  5. washThe extract was washed with dilute hydrochloric acid
  6. dry with materialan aqueous solution of sodium bicarbonate and then an aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customThe resulting crude product was chromatographed on a silica gel column

Sources & evidence

ORD record
ord-d324304a15914608bfbbcf80e9d86b7a
Source dataset
uspto-grants-1984_08
Patent number
US04466980

Reaction notes

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