Diisopropyl azodicarboxylate → HCID 18447000, compound

HRID 1268990Notes

Reaction equation

HRID 1268990 reaction equation
[CH:1]1([C:4]2[NH:8][N:7]=[N:6][N:5]=2)[CH2:3][CH2:2]1.[O:9]=[S:10]1(=[O:36])[CH2:15][CH:14]=[C:13]([C:16]2[C:21]([F:22])=[CH:20][C:19]([N:23]3[CH2:27][C@H:26]([CH2:28]OS(C)(=O)=O)[O:25][C:24]3=[O:34])=[CH:18][C:17]=2[F:35])[CH2:12][CH2:11]1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>>[O:36]=[S:10]1(=[O:9])[CH2:11][CH:12]=[C:13]([C:16]2[C:21]([F:22])=[CH:20][C:19]([N:23]3[CH2:27][CH:26]([CH2:28][N:6]4[N:7]=[N:8][C:4]([CH:1]5[CH2:3][CH2:2]5)=[N:5]4)[O:25][C:24]3=[O:34])=[CH:18][C:17]=2[F:35])[CH2:14][CH2:15]1

Participants

4

Reactant 3

HCID 5363146Diisopropyl azodicarboxylateHCID 11224380HCID 11224380, compoundHCID 178419788HCID 178419788, compound

Product 1

HCID 18447000HCID 18447000, compoundYield 74%

Procedure

Cyclopropylcarbonitrile (2 ml, 27 mmol) was added to a solution of trimethylsilylazide (4.3 ml, 32.5 mmol) and trimethylaluminum (16 ml of a 2M toluene solution, 32 mmol) at 0° C. The cold bath was removed, the mixture was stirred at room temperature for 15 minutes, then warmed to 80° C. for 16 hours. The solution was carefully added to a slurry of ice and 1N HCl, followed by acidification with concentrated HCl and extraction twice with ethyl acetate. The combined organic phases were washed with saturated NaCl, dried over sodium sulfate, and evaporated to yield a solid residue. Trituration with 1:1 hexane:ethyl acetate gave 5-cyclopropyl-1H-tetrazole (CAS# 27943–07–3) as a white crystalline solid (1.5 g, 51%). 5-cyclopropyl-1H-tetrazole (0.183 g, 1.66 mmol), (5R)-3-[4-(1,1-dioxo-3,6-dihydro-2H-thiopyran-4-yl)-3,5-difluorophenyl]-5-(hydroxymethyl)-1,3-oxazolidin-2-one (WO 01/81350 A1) (0.30 g, 0.84 mmol), polystyrene-triphenylphosphine (1.73 mmol/g loading: Argonaut Technologies, Inc. Foster City, Calif. USA, 1.46 g, 2.53 mmol) and diisopropylazodicarboxylate (0.33 ml, 1.68 mmol) were reacted as described for Example 58. Purification was carried out by chromatography on silica gel with 10% acetonitrile in dichloromethane. The material obtained after chromatography was precipitated from dichloromethane solution with ether to yield the title compound as a white powder (0.28 g, 74%).

Workup

  1. customPurification
  2. customThe material obtained after chromatography
  3. customwas precipitated from dichloromethane solution with ether

Sources & evidence

ORD record
ord-742a7aa203394780a1de2ce2fc34675a
Source dataset
uspto-grants-2007_04
Patent number
US07199143B2

Reaction notes

Loading…