Azide → Sinefungin

HRID 2273053Notes

Reaction equation

HRID 2273053 reaction equation
[NH2:1][C@@H:2]([CH2:6][CH2:7][C@H:8]([NH2:30])[CH2:9][C@@H:10]1[C@@H:14]([OH:15])[C@@H:13]([O:16]CC#C)[C@H:12]([N:20]2[CH:28]=[N:27][C:26]3[C:21]2=[N:22][CH:23]=[N:24][C:25]=3[NH2:29])[O:11]1)[C:3]([OH:5])=[O:4].O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+].[N-]=[N+]=[N-].C(#N)C.O.C(O)(C(F)(F)F)=O>O.CN(C=O)C.S([O-])([O-])(=O)=O.[Cu+2].CO.O.CC(O)=O>[CH:23]1[N:24]=[C:25]([NH2:29])[C:26]2[N:27]=[CH:28][N:20]([C@@H:12]3[O:11][C@H:10]([CH2:9][C@@H:8]([NH2:30])[CH2:7][CH2:6][C@H:2]([NH2:1])[C:3]([OH:5])=[O:4])[C@@H:14]([OH:15])[C@H:13]3[OH:16])[C:21]=2[N:22]=1

Participants

9

Reactant 4

HCID 33558Azide2×HCID 22145617Water TFA acetonitrile2×HCID 23667548Sodium AscorbateHCID 86673677HCID 86673677, compound

Product 1

HCID 65482SinefunginYield 13%

Reagents, catalysts & solvents 4

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent3×HCID 6228DimethylformamideSolventHCID 86607755Acetic acid methanol waterSolvent2×

Procedure

To a mixture consisting of Compound 7 (˜671 μg, 0.0016 mmol) in water (100 μL) with sodium ascorbate (1 mg, 0.005 mmol) in water (200 μL) was added copper(II) sulfate (500 μg, 0.0031 mmol) in water (100 μL) and CAL Fluor® Red 610 azide (Biosearch Technologies, Inc. Lot #MVR1716, 1.4 mg, 0.0016 mmol) in DMF (400 μL). The reaction mixture was stirred at room temperature overnight. HPLC (Gemini C18, 110 {acute over (Å)}, 5μ, 250×4.6 mm, 1 mL/min, 5/95/0.05→90/10/0.05 ACN/H2O/TFA) showed mainly one product (13.2 min, 21%) and starting fluorophore azide (19.6 min, 60%). Prep HPLC (Gemini C18, 110 {acute over (Å)}, 10μ, 250×21.2 mm, 20 mL/min, 15/85/0.05→90/10/0.05 ACN/H2O/TFA) was done to purify the product which eluted from the column at around 9 min. The product solution was concentrated to remove the ACN and then lyophilized to afford the title detection analyte compound (248 μg as quantified by UV (MeOH, extinction coefficient 91,000), 13% yield) as a dark purple solid; LC/MS (Gemini C18, 3μ, 2.0×50 mm, 400 μL/min, A: 90/10/0.01 H2O/MeOH/HOAc, B 90/10/0.01 MeOH/H2O/HOAc 0-6 min 0-100% B, 6-9 hold at 100% B, 9.1-15 min re-equilibrate at 0% B) consistent with that expected for pure title detection analyte compound (5.2 min, ESI+ m/z=1162/2=581).

Workup

  1. customone product (13.2 min, 21%)
  2. customto purify the product which
  3. washeluted from the column at around 9 min
  4. concentrationThe product solution was concentrated
  5. customto remove the ACN
  6. customto afford the title detection analyte compound (248 μg as quantified by UV (MeOH, extinction coefficient 91,000), 13% yield) as a dark purple solid
  7. customat 100% B, 9.1-15 min
  8. customdetection analyte compound (5.2 min, ESI+ m/z=1162/2=581)

Sources & evidence

ORD record
ord-180633d299494a118414c055c6b18d00
Source dataset
uspto-grants-2015_09
Patent number
US09120820B2

Reaction notes

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