Sodium Cyanide → HCID 59465470, compound

HRID 547582Notes

Reaction equation

HRID 547582 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:13](=[O:14])[C:12]3[CH:15]=[CH:16][CH:17]=[N:18][C:11]=3[N:10]=[C:9]2[C@H:19]([NH:21][C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:20])=[CH:4][CH:3]=1.[C-:29]#[N:30].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:29]([C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:13](=[O:14])[C:12]3[CH:15]=[CH:16][CH:17]=[N:18][C:11]=3[N:10]=[C:9]2[C@H:19]([NH:21][C:22](=[O:28])[O:23][C:24]([CH3:25])([CH3:26])[CH3:27])[CH3:20])=[CH:4][CH:3]=1)#[N:30]

Participants

5

Reactant 2

HCID 8929Sodium CyanideHCID 59465467HCID 59465467, compound

Product 1

HCID 59465470HCID 59465470, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
70 °C

Procedure

Compound 15 (2.02 g, 4.10 mmol), prepared as described in Section 7.11, was combined with (Ph3P)4Pd (439 mg, 0.38 mmol), CuI (157 mg, 0.82 mmol) and NaCN (406 mg, 8.29 mmol) in a 25 mL pear shaped flask equipped with a reflux condenser. The mixture was evacuated under high vacuum and backfilled with dry N2 three times. Acetonitrile (6 mL) was then added and the resulting suspension heated to 70° C. for 30 min. at which point TLC and HPLC analysis indicated near complete consumption of 15. The mixture was diluted with EtOAc (100 mL) and filtered through a pad of celite. The filtrate was washed with saturated NaHCO3 (100 mL). The aqueous wash was extracted with additional EtOAc (2×50 mL). The combined extracts were dried over Na2SO4 and concentrated. Purification of the residue by silica gel chromatography (50×400 mm column; 80% EtOAc/hexanes to 100% EtOAc) gave 16 (1.42 g, 89%; purity 96% AUC; 92% e.e. by chiral HPLC analysis). Rf=0.35 (80% EtOAc/hexanes).

Workup

  1. customequipped with a reflux condenser
  2. customThe mixture was evacuated under high vacuum and backfilled with dry N2 three times
  3. additionAcetonitrile (6 mL) was then added
  4. customindicated near complete consumption of 15
  5. additionThe mixture was diluted with EtOAc (100 mL)
  6. filtrationfiltered through a pad of celite
  7. washThe filtrate was washed with saturated NaHCO3 (100 mL)
  8. washThe aqueous wash
  9. extractionwas extracted with additional EtOAc (2×50 mL)
  10. dry with materialThe combined extracts were dried over Na2SO4
  11. concentrationconcentrated
  12. customPurification of the residue by silica gel chromatography (50×400 mm column; 80% EtOAc/hexanes to 100% EtOAc)

Sources & evidence

ORD record
ord-90c618a956884745b94d7577bbf0315d
Source dataset
uspto-grants-2011_05
Patent number
US07939538B2

Reaction notes

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