Trifluoromethanesulfonic acid → HCID 86755670, compound

HRID 1872458Notes

Reaction equation

HRID 1872458 reaction equation
[CH2:1]([O:3][C:4]([C@@H:6]1[C@@H:11]2[C@H:7]1[CH2:8][C@@H:9]([OH:25])[C@@:10]2([N:22]=[N+:23]=[N-:24])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])=[O:5])[CH3:2].ClC(Cl)(Cl)C(=N)O[CH2:30][CH:31]=[CH2:32].S(O)(C(F)(F)F)(=O)=O>C1CCCCC1.CCOCC>[CH2:1]([O:3][C:4]([C@@H:6]1[C@@H:11]2[C@H:7]1[CH2:8][C@@H:9]([O:25][CH2:32][CH:31]=[CH2:30])[C@@:10]2([N:22]=[N+:23]=[N-:24])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 62406Trifluoromethanesulfonic acidHCID 316905Allyl 2,2,2-TrichloroacetimidateHCID 11772339HCID 11772339, compound

Product 1

HCID 86755670HCID 86755670, compoundYield 14%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8078CyclohexaneSolvent

Procedure

To a solution of (1S,2R,3R,5R,6S)-2-azido-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid 2-benzyl ester 6-ethyl ester (VII) (200 mg, 0.58 mmol) and allyl 2,2,2-trichloroacetimidate (0.18 mL, 1.16 mmol) in cyclohexane (0.7 mL) was added TfOH (29 □L), whereupon the solution became hot and stirring was continued at 23° C. for 1 h. The reaction mixture was poured on ice, diluted with ether, washed with sat. NaHCO3 -sol., brine and dried over MgSO4. The crude product was purified by silica gel column chromatography with hexane/EtOAc 4:1 to give (1S,2R,3R,5R,6S)-3-allyloxy-2-azido-bicyclo [3.1.0]hexane-2,6-dicarboxylic acid 2-benzyl ester 6-ethyl ester (XXIII-2) (31 mg, 14%) as a yellow oil. 1H-NMR (250 MHz, CDCl3) □1.26 (3H, t, J=7.1 Hz), 1.76 (1H, t, J=3.5 Hz), 2.03-2.26 (3H, m), 2.32 (1H, dd, J=12, 7 Hz), 3.58 (1H, dd, J=9, 7 Hz), 3.92 (1H, m), 4.02 (1H, m), 4.13 (2H, q, J=7.1 Hz), 5.10-5.22 (2H, m), 5.25 (1H, d,J=12 Hz), 5.34 (1H, d,J=12 Hz), 5.75 (1H, m), 7.30-7.42 (5H, m);MS[EI] 284 [(M-CO2Et-N2)+ ]; □D20 17.85° (c=0.50, CHCl3).

Workup

  1. additionThe reaction mixture was poured on ice
  2. washwashed with sat. NaHCO3 -sol
  3. dry with material, brine and dried over MgSO4
  4. customThe crude product was purified by silica gel column chromatography with hexane/EtOAc 4:1

Sources & evidence

ORD record
ord-3b83fe72c8a24bd2838f48f0cbe0e4a5
Source dataset
uspto-grants-2000_08
Patent number
US06107342

Reaction notes

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