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

HRID 544852Notes

Reaction equation

HRID 544852 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 successively 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 successively 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-8709c9a339934d1fb9982e9c0f6ed357
Source dataset
uspto-grants-2011_05
Patent number
US07935686B2

Reaction notes

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