2,6-Di-tert-butylpyridine → HCID 90408960, compound

HRID 1855096Notes

Reaction equation

HRID 1855096 reaction equation
[O:1]([C:8]1[CH:9]=[C:10]([C:14]23[CH2:21][CH2:20][C:17]([OH:22])([CH2:18][CH2:19]2)[CH2:16][O:15]3)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH2:24]/[CH:25]=[CH:26]/[C:27]([O:29][CH3:30])=[O:28].C(C1C=CC=C(C(C)(C)C)N=1)(C)(C)C>C(Cl)Cl.C(S([O-])(=O)=O)(F)(F)F.[Ag+]>[O:1]([C:8]1[CH:9]=[C:10]([C:14]23[CH2:21][CH2:20][C:17]([O:22][CH2:24]/[CH:25]=[CH:26]/[C:27]([O:29][CH3:30])=[O:28])([CH2:18][CH2:19]2)[CH2:16][O:15]3)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 685102,6-Di-tert-butylpyridineHCID 53691752-Butenoic acid, 4-bromo-, methyl esterHCID 90408723HCID 90408723, compound

Product 1

HCID 90408960HCID 90408960, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 76223Silver(I) trifluoromethanesulfonateCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 96C [1-(3-phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-ol] (63 mg, 0.213 mmol), methyl 4-bromocrotonate (0.075 mL, 0.64 mmol), 2,6-di-tert-butylpyridine (0.334 mL, 1.49 mmol), and AgOTf (164 mg, 0.64 mmol) in DCM (0.5 mL) was stirred at rt in the dark for 3 days. LC-MS showed the presence of the product, and the reaction was filtered. The filtrate was concentrated in vacuo. The crude product was chromatographed [SiO2; continuous gradient of EtOAc/hexane (0% to 10% over 10 min)] to give the title compound (42 mg, 0.106 mmol, 50% yield) as an oil. 1H NMR (CDCl3) δ: 7.28-7.17 (m, 3H), 7.07-6.98 (m, 3H), 6.94-6.86 (m, 3H), 6.78 (ddd, J=8.1, 2.4, 1.0 Hz, 1H), 6.02 (dt, J=15.6, 2.2 Hz, 1H), 4.07 (dd, J=4.2, 2.1 Hz, 2H), 3.84 (t, J=1.4 Hz, 2H), 3.67 (s, 3H), 2.11-2.03 (m, 4H), 1.97-1.88 (m, 2H), 1.86-1.77 (m, 2H).

Workup

  1. filtrationthe reaction was filtered
  2. concentrationThe filtrate was concentrated in vacuo
  3. customThe crude product was chromatographed [SiO2; continuous gradient of EtOAc/hexane (0% to 10% over 10 min)]

Sources & evidence

ORD record
ord-863fd70e7fe148d18f4d0534e5f346f7
Source dataset
uspto-grants-2015_02
Patent number
US08962660B2

Reaction notes

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