Potassium Phosphate, Tribasic → (1R,10R,11S,16S)-5-methoxy-1,3,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

HRID 422141Notes

Reaction equation

HRID 422141 reaction equation
FC(F)(F)S(O[C:7]1[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]2[C:8]=1[C@@:9]1([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]1)(=O)=O.[CH3:33]B1OB(C)OB(C)O1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>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.O1CCOCC1>[CH3:26][O:25][C:23]1[CH:22]=[C:21]2[C:8]([C@@:9]3([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]3)=[C:7]([CH3:33])[CH:24]=1

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 574072TrimethylboroxineHCID 53241983(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate

Product 1

HCID 53241984(1R,10R,11S,16S)-5-methoxy-1,3,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trieneYield 83.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

In a sealed tube was placed (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate (Compound No. 32) (0.098 g, 0.20 mmol), trimethylboroxine (0.050 g, 0.40 mmol), K3PO4 (0.085 g, 0.40 mmol), Pd(Ph3P)4 (0.046 g, 0.04 mmol) and dioxane (4 mL). The vessel was degassed for 5 min, then sealed and stirred at 100° C. for 16 h. The reaction was cooled to room temperature, diluted with EtOAc and washed with brine. The organic layer was separated, dried (Na2SO4) and concentrated. Purification by column chromatography on silica gel (Hexanes/EtOAc, 95:5) gave (1R,10R,11S,16S)-5-methoxy-1,3,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 33) (0.060 g, 83%) as a white foam. 1H NMR (CDCl3): δ 6.46 (m, 1H), 6.39 (m, 1H), 3.71 (s, 3H), 2.98-2.80 (m, 3H), 2.50 (s, 3H), 1.95-1.37 (m, 8H), 1.37 (s, 3H), 1.20-1.00 (m, 2H), 0.94 (s, 3H), 0.90 (m, 1H), 0.86 (s, 3H), 0.84 (s, 3H). MS m/z 359 (C23H34OS+H+).

Workup

  1. customIn a sealed tube was placed
  2. customThe vessel was degassed for 5 min
  3. customsealed
  4. temperatureThe reaction was cooled to room temperature
  5. additiondiluted with EtOAc
  6. washwashed with brine
  7. customThe organic layer was separated
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated
  10. customPurification by column chromatography on silica gel (Hexanes/EtOAc, 95:5)

Sources & evidence

ORD record
ord-587fd3f319e34f73a2223603f2f36f64
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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