Sodium borohydride → 1-t-Butyldimethylsilyl-4-tritylthio-2-azetidinone

HRID 355260Notes

Reaction equation

HRID 355260 reaction equation
[Si:1]([N:8]1[CH:11]([S:12][C:13]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:10](C(=O)CC)[C:9]1=[O:36])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[BH4-].[Na+]>C1COCC1>[Si:1]([N:8]1[CH:11]([S:12][C:13]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH2:10][C:9]1=[O:36])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 205054601-t-Butyldimethylsilyl-3-propionyl-4-tritylthio-2-azetidinone

Product 1

HCID 129287451-t-Butyldimethylsilyl-4-tritylthio-2-azetidinoneYield 47%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1-t-butyldimethylsilyl-3-proprionyl-4-tritylthio-2-azetidinone (26 g, 50 mmol) and sodium borohydride (7.6 g, 200 mmol) in THF (400 ml) was stirred at room temperature for 18 h. It was poured onto ice-HCl (1N) (pH 6) and extracted with ether. The acidic phase was extracted several times with ether and the combined ether solution was washed with brine, dried (Na2SO4) and evaporated to give an amorphous solid, 25.0 g. This crude product was chromatographed on SiO2 (ACT. 1, 400 g) and eluted first with CH2Cl2 to give 10.8 g of 1-t-butyldimethylsilyl-4-tritylthio-2-azetidinone. Elution with 20% ether in CH2Cl2 gave 10.3 g of the title compound as a mixture of two isomeric trans alcohols. This was separated by hplc (Water Associates, System 500), and using 10% EtOAc in CH2Cl2 as eluent. Isomer C, white solid, 3.8 g; mp (pet. ether) 134°-36° C. 1Hmr (CDCl3) δ: 7.1-7.8 (15H, m, STr), 4.35 (H, d), 3.1 (H, dd), 2.5 (H, m), 0.7-1.7 (5H, m), 0.97 (9H, s) and 0.25 ppm (6H, s). Anal. calcd for C31H39NO2SSi: C 71.91, H 7.59, N 2.71; found: C 71.51, H 7.60, N 2.96. Isomer B, white solid, 5.4 g; mp (pentane-pet. ether) 97°-99° C. 1Hmr (CDCl3) δ: 7.1-7.8 (15H, m, STr), 4.15 (H, d), 3.4 (H, dd), 3.2 (H, m), 0.7-1.7 (5H, m), 0.85 (9H, s) and 0.1 ppm (6H, s). Total yield of these two alcohols (based on recovered starting material was 67.5%.

Workup

  1. additionIt was poured onto ice-HCl (1N) (pH 6)
  2. extractionextracted with ether
  3. extractionThe acidic phase was extracted several times with ether
  4. washthe combined ether solution was washed with brine
  5. dry with materialdried (Na2SO4)
  6. customevaporated
  7. customto give an amorphous solid, 25.0 g
  8. customThis crude product was chromatographed on SiO2 (ACT. 1, 400 g)
  9. washeluted first with CH2Cl2

Sources & evidence

ORD record
ord-55d285df1eb14e338c2748647bc95963
Source dataset
uspto-grants-1983_03
Patent number
US04378314

Reaction notes

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