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

HRID 230609Notes

Reaction equation

HRID 230609 reaction equation
C(=O)(SC)O[O:3][CH:4]([O:8][C:9](=[O:13])[CH:10]([CH3:12])[CH3:11])[CH:5]([CH3:7])[CH3:6].[OH:17][N:18]1[C:22](=[O:23])[C@H:21]([O:24][C:25](=[O:32])[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:20]([O:33][C:34](=[O:41])[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:19]1=[O:42].[C:43](OO)(=[O:45])C.C(O)(=O)C>ClCCCl>[CH3:12][CH:10]([CH3:11])[C:9]([O:8][C@@H:4]([O:3][C:43]([O:17][N:18]1[C:22](=[O:23])[C@H:21]([O:24][C:25](=[O:32])[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C@@H:20]([O:33][C:34](=[O:41])[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:19]1=[O:42])=[O:45])[CH:5]([CH3:6])[CH3:7])=[O:13]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 6585Peracetic AcidHCID 111319931-Hydroxy-(3R,4R)-2,5-Dioxo-3,4-dibenzoyloxypyrrolidineHCID 86598004O-(1-Isobutanoyloxyisobutoxy) S-Methyl Thiocarbonate

Product 1

HCID 11706554(1S)-1-[((3R,4R)-2,5-Dioxo-3,4-dibenzoyloxypyrrolidinyl)-oxycarbonyloxy]-2-methylpropyl 2-methylpropanoateYield 25%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
15 °C

Procedure

A 3 L three necked round bottom flask fitted with a mechanical stirrer, Teflon coated temperature probe and an addition funnel was charged with compound (11) (234 g, 1 mol), compound (30) (330 g, 0.95 mol), and 1,2-dichloroethane (2200 mL). The reaction mixture was cooled under a nitrogen atmosphere in an ice water bath to 15° C. To the stirred reaction mixture was added a 39% solution of peracetic acid in dilute acetic acid (500 mL, 2.94 mol) over 2 h, maintaining the temperature between 15° C. and 22° C. This temperature was maintained for an additional 12 h during which time a white precipitate was formed. The reaction mixture was further cooled to 3-4° C., the product collected by filtration, and washed with hexane (2×1 L). The product was dried in vacuo, yielding the title compound (28) (128 g, 0.24 mol, 25% yield). The diastereomeric purity of the product was determined to be >99% d.e. by HPLC using a chiral column. 1H NMR (CDCl3, 400 MHz): δ 1.0 (d, 6H), 1.2 (dd, 6H), 2.1 (m, 1H), 2.65 (m, 1H), 6.0 (br. s, 2H), 6.6 (d, 1H), 7.45 (app. t, 4H), 7.65 (app. t, 2H), 8.05 (d, 4H).

Workup

  1. customTo the stirred reaction mixture
  2. temperaturemaintaining the temperature between 15° C. and 22° C
  3. temperatureThis temperature was maintained for an additional 12 h during which time a white precipitate
  4. customwas formed
  5. temperatureThe reaction mixture was further cooled to 3-4° C.
  6. filtrationthe product collected by filtration
  7. washwashed with hexane (2×1 L)
  8. customThe product was dried in vacuo

Sources & evidence

ORD record
ord-74a4244ff93642d2ac6c5311fa2ef422
Source dataset
uspto-grants-2009_07
Patent number
US07566738B2

Reaction notes

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