Potassium Bromide → tert-Butyl 3,5-dideoxy-2,4-O-(1-methylethylidene)-L-erythro-hexuronate

HRID 1373357Notes

Reaction equation

HRID 1373357 reaction equation
[Br-].[K+].C(=O)(O)[O-].[Na+].[OH:8][CH2:9][C@H:10]1[O:15][C:14]([CH3:17])([CH3:16])[O:13][C@@H:12]([CH2:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:11]1.Cl[O-].[Na+]>C(Cl)Cl>[C:22]([O:21][C:19](=[O:20])[CH2:18][C@H:12]1[CH2:11][C@@H:10]([CH:9]=[O:8])[O:15][C:14]([CH3:17])([CH3:16])[O:13]1)([CH3:23])([CH3:25])[CH3:24]

Participants

6

Reactant 4

HCID 253877Potassium BromideHCID 516892Sodium Bicarbonate2×HCID 9816650tert-Butyl 2,4-dideoxy-3,5-O-(1-methylethylidene)-D-erythro-hexonateHCID 23665760Sodium Hypochlorite2×

Product 1

HCID 9881588tert-Butyl 3,5-dideoxy-2,4-O-(1-methylethylidene)-L-erythro-hexuronate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

2,2,6,6-tetramethyl piperidinyl oxy free radical (TEMPO) (0.2 g), potassium bromide (9.6 g) and sodium bicarbonate (90 g) were dissolved in methylene chloride (600 ml) and stirred the contents together at 0–5° C. A solution of (4R-cis)-6-(hydroxymethyl)-2,2-dimethyl-1,3-dioxane-4-acetic acid, 1,1-dimethylethyl ester of Formula III (100 g) in methylene chloride (400 ml) was added to the above solution at 0–5° C. To this solution 10% sodium hypochlorite solution (159 ml) (NaOCl) was added at 0–5° C. Again sodium bicarbonate (96 g) and followed by 10% sodium hypochlorite solution was added to the reaction mass. Reaction mass was maintained for 1–2 hours at 0–5° C. and filtered through perlite. The organic layer was separated and washed with 10% sodium thiosulfate solution (250 ml), then water (250 ml) followed by saturated sodium chloride solution (250 ml). Organic layer was distilled at below 40° C. under reduced pressure to afford the title product. Yield: 95 g.

Workup

  1. additionwas added to the reaction mass
  2. customReaction mass
  3. temperaturewas maintained for 1–2 hours at 0–5° C.
  4. filtrationfiltered through perlite
  5. customThe organic layer was separated
  6. washwashed with 10% sodium thiosulfate solution (250 ml)
  7. distillationOrganic layer was distilled at below 40° C. under reduced pressure

Sources & evidence

ORD record
ord-42c7fd1d894e4ecebd2cf815d521fa36
Source dataset
uspto-grants-2007_01
Patent number
US07161004B2

Reaction notes

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