Allyl 2-{(3R,4S)-3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[2-(5-ethyl-1-methylpyrazol-3-yl)-2-oxoethyl]azetidin-2-on-1-yl}-2-(tri-n-butylphosphoranylidene)acetate → Allyl (5R,6S)-2-(5-Ethyl-1-methylpyrazol-3-yl)-6-[(R)-1-hydroxyethyl]carbapen-2-em-3-carboxylate

HRID 977009Notes

Reaction equation

HRID 977009 reaction equation
[Si]([O:8][C@@H:9]([C@H:11]1[C@H:14]([CH2:15][C:16]([C:18]2[CH:22]=[C:21]([CH2:23][CH3:24])[N:20]([CH3:25])[N:19]=2)=O)[N:13]([C:26](=P(CCCC)(CCCC)CCCC)[C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28])[C:12]1=[O:46])[CH3:10])(C(C)(C)C)(C)C>C1(C)C=CC=CC=1>[CH2:23]([C:21]1[N:20]([CH3:25])[N:19]=[C:18]([C:16]2[CH2:15][C@@H:14]3[C@@H:11]([C@H:9]([OH:8])[CH3:10])[C:12](=[O:46])[N:13]3[C:26]=2[C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28])[CH:22]=1)[CH3:24]

Participants

3

Reactant 1

HCID 87937932Allyl 2-{(3R,4S)-3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[2-(5-ethyl-1-methylpyrazol-3-yl)-2-oxoethyl]azetidin-2-on-1-yl}-2-(tri-n-butylphosphoranylidene)acetate

Product 1

HCID 131719868Allyl (5R,6S)-2-(5-Ethyl-1-methylpyrazol-3-yl)-6-[(R)-1-hydroxyethyl]carbapen-2-em-3-carboxylate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Allyl 2-{(3R,4S)-3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[2-(5-ethyl-1-methylpyrazol-3-yl)-2-oxoethyl]azetidin-2-on-1-yl}-2-(tri-n-butylphosphoranylidene)acetate (1.94 g) in toluene (650 ml; 3 mgs/ml) was heated under reflux for a total of 7 h. T.l.c. analysis showed only a small mount of unreacted starting material. The solution was concentrated and purified by silica gel chromatography, eluting with 5% then 10% acetone/ethyl acetate. The product was obtained as an off white, crystalline solid. Trimration with ether, followed by filtration gave the title compound as a colourless crystalline solid, (356 mg; 30% ); (Found: M+, 345.1689. C18H23N3O4 requires M 345.1689); nmax (CH2Cl2) 3603, 1774, 1716, 1599(w) and 1542(w) cm-1 ; dH (CDCl3) 1.28 (3H, t, J7.4 Hz), 1.36 (3H, d, J6.3 Hz), 1.85 (1H, d, J5.0 Hz), 2.61 (2H, d, J7.4 Hz), 3.19 (1H, dd, J2.8,6.7 Hz), 3.27 (1H, dd, J9.0,18.5 Hz), 3.59 (1H, dd, J9.8,18.5 Hz), 3.84 (3H, s), 4.24 (2H, m), 4.79 (2H, m), 5.27 (1H, m), 5.46 (1H, m), 6.01 (1H, m) and 7.02 (1H, s).

Workup

  1. temperatureunder reflux for a total of 7 h
  2. concentrationThe solution was concentrated
  3. custompurified by silica gel chromatography
  4. washeluting with 5%
  5. customThe product was obtained as an off white, crystalline solid
  6. filtrationTrimration with ether, followed by filtration

Sources & evidence

ORD record
ord-b14e5885ac2e4605a379c488666fc9cb
Source dataset
uspto-grants-1997_03
Patent number
US05612477

Reaction notes

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