Peracetic Acid → (1R)-1-[((3S,4S)-2,5-Dioxo-3,4-dibenzoyloxypyrrolidinyl)-oxycarbonyloxy]-2-methylpropyl 2-methylpropanoate

HRID 230606Notes

Reaction equation

HRID 230606 reaction equation
[OH:1][N:2]1[C:6](=[O:7])[C@@H:5]([O:8][C:9](=[O:16])[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C@H:4]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:3]1=[O:26].C(=O)(SC)O[O:29][CH:30]([O:34][C:35](=[O:39])[CH:36]([CH3:38])[CH3:37])[CH:31]([CH3:33])[CH3:32].[C:43](OO)(=[O:45])C>ClCCl.C(O)(=O)C>[CH3:38][CH:36]([CH3:37])[C:35]([O:34][C@H:30]([O:29][C:43]([O:1][N:2]1[C:6](=[O:7])[C@@H:5]([O:8][C:9](=[O:16])[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)[C@H:4]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:3]1=[O:26])=[O:45])[CH:31]([CH3:32])[CH3:33])=[O:39]

Participants

6

Reactant 3

HCID 6585Peracetic Acid2×HCID 122748841-Hydroxy-(3S,4S)-2,5-Dioxo-3,4-dibenzoyloxypyrrolidineHCID 86598004O-(1-Isobutanoyloxyisobutoxy) S-Methyl Thiocarbonate

Product 1

HCID 11663877(1R)-1-[((3S,4S)-2,5-Dioxo-3,4-dibenzoyloxypyrrolidinyl)-oxycarbonyloxy]-2-methylpropyl 2-methylpropanoateYield 25.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of compound (27) (35 g, 98.6 mmol) and thiocarbonate (11) (34.6 g, 148 mmol) in dichloromethane at 0° C. was dropwise added a 32% solution of peracetic acid (300 mmol) in acetic acid over 2 h. The reaction temperature was kept below 35° C. during the addition of peracetic acid. After the addition was complete, the reaction mixture was stirred overnight at room temperature. The resulting white precipitate was filtered and washed sequentially with water and a mixture of ether and hexane (1:2), then dried under vacuum to afford the crude title compound. This product was crystallized once from a mixture of ethyl acetate and hexane (1:1) to afford the title compound (25) (13.7 g, 25% yield). The diastereomeric purity of the product was determined to be 98.4% d.e. by HPLC using a chiral column. 1H NMR (CDCl3, 400 MHz): δ 1.06 (d, 6H), 1.22 (d, 3H), 1.22 (d, 3H), 2.20 (m, 1H), 2.64 (hept., 1H), 6.01 (br. s, 2H), 6.64 (d, 1H), 7.47 (m, 4H), 7.63 (m, 2H), 8.07 (m, 4H).

Workup

  1. additionAfter the addition
  2. filtrationThe resulting white precipitate was filtered
  3. washwashed sequentially with water
  4. additiona mixture of ether and hexane (1:2)
  5. customdried under vacuum
  6. customto afford the crude title compound
  7. customThis product was crystallized once from a mixture of ethyl acetate and hexane (1:1)

Sources & evidence

ORD record
ord-52808aad924a46c9a3d7329879c0aeea
Source dataset
uspto-grants-2009_07
Patent number
US07566738B2

Reaction notes

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