Tetrahydrofuran → HCID 86701321, compound

HRID 1627047Notes

Reaction equation

HRID 1627047 reaction equation
[C:1]([O:5][C:6]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([OH:25])[C@@H:20]([OH:26])[C@H:19]([CH3:27])[O:18][C:17]1=[O:28])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)(OC(C)(C)C)O[CH2:31][CH:32]=[CH2:33].[CH2:40]1[CH2:44]OC[CH2:41]1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[C:11]([O:10][C:9]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([O:25][CH2:33][CH:32]=[CH2:31])[C@@H:20]([O:26][CH2:44][CH:40]=[CH2:41])[C@H:19]([CH3:27])[O:18][C:17]1=[O:28])[C:6](=[O:7])[O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:15])([CH3:14])([CH3:13])[CH3:12]

Participants

6

Reactant 3

HCID 8028TetrahydrofuranHCID 11194471ALLYL TERT-BUTYL CARBONATEHCID 86701319HCID 86701319, compound

Product 1

HCID 86701321HCID 86701321, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
60 °C

Procedure

To a stirred solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]carbamate (170 mg, 0.419 mmol), Pd2(dba)3 (38.4 mg, 0.042 mmol) and dppf (46.5 mg, 0.084 mmol) in anhydrous THF (4.0 mL) was added allyl tert-butyl carbonate (332 mg, 2.096 mmol) and the resulting mixture was warmed to 60° C. and stirred for 1 h. The reaction was concentrated and the residue purified by flash chromatography (SiO2, EtOAc/hexanes) to yield the title compound as a light yellow oil (170 mg, 83%): 1H NMR (400 MHz, CDCl3) δ 6.02-5.78 (m, 2H), 5.30-5.10 (m, 5H), 4.81 (dq, J=9.5, 6.3 Hz, 1H), 4.38 (ddd, J=12.2, 5.5, 1.4 Hz, 1H), 4.24 (dd, J=12.1, 4.1 Hz, 1H), 4.17-4.02 (m, 3H), 3.95-3.81 (m, 2H), 3.54 (dd, J=10.9, 7.2 Hz, 1H), 3.41-3.21 (m, 2H), 1.50 (s, 18H), 1.42 (d, J=6.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 169.00, 152.64, 134.93, 134.80, 116.95, 116.78, 84.63, 83.06, 82.84, 75.93, 74.68, 72.85, 72.62, 71.85, 57.94, 27.97, 18.74; ESIMS m/z 509.2 ([M+Na]+).

Workup

  1. concentrationThe reaction was concentrated
  2. customthe residue purified by flash chromatography (SiO2, EtOAc/hexanes)

Sources & evidence

ORD record
ord-577fda2a16db4c1cb6fa4f4d93fbca8b
Source dataset
uspto-grants-2014_07
Patent number
US08785479B2

Reaction notes

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