Boron tribromide → (1R,10R,11S,16S)-5-hydroxy-N,1,11,15,15-pentamethyl-8-thiatetracyclo-[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxamide

HRID 422170Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 422170
C[O:2][C:3]1[CH:20]=[C:19]2[C:6]([C@@:7]3([CH3:24])[C@H:16]([CH2:17][S:18]2)[C@:15]2([CH3:21])[C@H:10]([C:11]([CH3:23])([CH3:22])[CH2:12][CH2:13][CH2:14]2)[CH2:9][CH2:8]3)=[C:5]([C:25]([NH:27][CH3:28])=[O:26])[CH:4]=1.B(Br)(Br)Br>C(Cl)Cl>[OH:2][C:3]1[CH:20]=[C:19]2[C:6]([C@@:7]3([CH3:24])[C@H:16]([CH2:17][S:18]2)[C@:15]2([CH3:21])[C@H:10]([C:11]([CH3:22])([CH3:23])[CH2:12][CH2:13][CH2:14]2)[CH2:9][CH2:8]3)=[C:5]([C:25]([NH:27][CH3:28])=[O:26])[CH:4]=1

Komponenten

4

Edukt 2

HCID 25134Boron tribromideHCID 58294801(1R,10R,11S,16S)-5-methoxy-N,1,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxamide

Produkt 1

HCID 58294828(1R,10R,11S,16S)-5-hydroxy-N,1,11,15,15-pentamethyl-8-thiatetracyclo-[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxamideAusbeute 57 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of (1R,10R,11S,16S)-5-methoxy-N,1,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxamide (75) (0.17 g, 0.42 mmol) in anhydrous CH2Cl2 (5.0 mL) was cooled with an ice bath under N2. To the mixture BBr3 (1 M in CH2Cl2, 1.6 mL, 1.6 mmol) was added dropwise. The mixture was stirred at 0° C. for 2.5 h then at room temperature for 3.25 h. The solution was cooled to 0° C. and quenched with anhydrous MeOH. The solution was evaporated and the residue co-evaporated with anhydrous MeOH. The solid was suspended in EtOAc and washed with 0.09 M HCl (11 mL). The mixture was taken to pH=7.5 using sodium bicarbonate. The organic layer was separated was concentrated to dryness. The crude material was triturated with MeOH then filtered and washed with MeOH to yield (1R,10R,11S,16S)-5-hydroxy-N,1,11,15,15-pentamethyl-8-thiatetracyclo-[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxamide (76) (0.09 g, 57%) as a white solid. 1H NMR (DMSO-d6): δ 9.37 (s, 1H), 8.10 (m, 1H), 6.36 (d, 1H), 6.18 (d, 1H), 2.94 (dd, 1H), 2.80 (d, 1H), 2.65 (d, 3H), 1.81 (d, 1H), 1.62-1.26 (m, 12H), 1.09 (ddd, 1H), 0.87-0.81 (m, 7H), 0.78 (s, 3H). MS m/z 388 (C23H33NO2S+H+).

Aufarbeitung

  1. waitat room temperature for 3.25 h
  2. temperatureThe solution was cooled to 0° C.
  3. customquenched with anhydrous MeOH
  4. customThe solution was evaporated
  5. washwashed with 0.09 M HCl (11 mL)
  6. customThe organic layer was separated
  7. concentrationwas concentrated to dryness
  8. customThe crude material was triturated with MeOH
  9. filtrationthen filtered
  10. washwashed with MeOH

Quellen und Nachweise

ORD-Eintrag
ord-5ca408624d354c9ca34163852ee39c63
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08101605B2

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