2,6-Lutidine → (2S,3S,5S,6R,8S)-8-allyl-6-(3-chlorophenyl)-5-(4-chlorophenyl)-3-ethyl-2,8-dimethyl-2,3,5,6,7,8-hexahydrooxazolo[3,2-a]pyridin-4-ium triflate

HRID 932106Notes

Reaction equation

HRID 932106 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C@@H:8]([CH2:18][C@:19]([C:24]2[O:25][C@@H:26]([CH3:31])[C@H:27]([CH2:29][CH3:30])[N:28]=2)([CH3:23])[CH2:20][CH:21]=[CH2:22])[C@H:9]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)O)[CH:5]=[CH:6][CH:7]=1.N1C(C)=CC=CC=1C.[F:40][C:41]([F:54])([F:53])[S:42]([O:45]S(C(F)(F)F)(=O)=O)(=[O:44])=[O:43]>C(Cl)Cl.[O-]S([O-])(=O)=O.[Cu+2]>[O-:45][S:42]([C:41]([F:54])([F:53])[F:40])(=[O:44])=[O:43].[CH2:20]([C@@:19]1([CH3:23])[CH2:18][C@H:8]([C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[CH:3]=2)[C@@H:9]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[N+:28]2[C@@H:27]([CH2:29][CH3:30])[C@H:26]([CH3:31])[O:25][C:24]1=2)[CH:21]=[CH2:22]

Participants

6

Reactant 3

HCID 79372,6-LutidineHCID 67749Trifluoromethanesulfonic anhydride2×HCID 66552262(1R,2R,4S)-2-(3-chlorophenyl)-1-(4-chlorophenyl)-4-((4S,5S)-4-ethyl-5-methyl-4,5-dihydrooxazol-2-yl)-4-methylhept-6-en-1-ol

Product 1

HCID 66552318(2S,3S,5S,6R,8S)-8-allyl-6-(3-chlorophenyl)-5-(4-chlorophenyl)-3-ethyl-2,8-dimethyl-2,3,5,6,7,8-hexahydrooxazolo[3,2-a]pyridin-4-ium triflate

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-50 °C

Procedure

To a solution of (1R,2R,4S)-2-(3-chlorophenyl)-1-(4-chlorophenyl)-4-((4S,5S)-4-ethyl-5-methyl-4,5-dihydrooxazol-2-yl)-4-methylhept-6-en-1-ol (80 mg, 0.174 mmol) in CH2Cl2 (1737 μl) at −50° C. was added 2,6-lutidine (46.4 μl, 0.400 mmol) followed by trifluoromethanesulfonic anhydride solution, 1 M in methylene chloride (191 μl, 0.191 mmol). The reaction was stirred at −50° C. for 30 min and then treated with an additional 25 uL of trifluoromethanesulfonic anhydride solution, 1 M in methylene chloride, then 2 mL of sat. CuSO4. The reaction was warmed to rt and extracted with dichloromethane. The organic phase was dried over MgSO4, filtered and concentrated. Purification by column chromatography using 40 to 80% acetone in hexanes afforded (2S,3S,5S,6R,8S)-8-allyl-6-(3-chlorophenyl)-5-(4-chlorophenyl)-3-ethyl-2,8-dimethyl-2,3,5,6,7,8-hexahydrooxazolo[3,2-a]pyridin-4-ium triflate.

Workup

  1. temperatureThe reaction was warmed to rt
  2. extractionextracted with dichloromethane
  3. dry with materialThe organic phase was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by column chromatography

Sources & evidence

ORD record
ord-f712211a6fcf42c1a7a95b86083b475e
Source dataset
uspto-grants-2016_03
Patent number
US09296736B2

Reaction notes

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