tert-Butanol → 6,7,8,9-Tetrahydro-5H-6,9-methanocyclohepta[b]pyridine-7,8-diol

HRID 272597Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 272597
[CH:1]12[CH2:12][CH:9]([CH:10]=[CH:11]1)[CH2:8][C:7]1[CH:6]=[CH:5][CH:4]=[N:3][C:2]2=1.[OH2:13].[OH2:14].C[N+]([O-])(C)C.C(O)(C)(C)C>ClCCl.[Os](=O)(=O)(=O)=O>[CH:1]12[CH2:12][CH:9]([CH:10]([OH:14])[CH:11]1[OH:13])[CH2:8][C:7]1[CH:6]=[CH:5][CH:4]=[N:3][C:2]2=1

Komponenten

6

Edukt 3

HCID 6386tert-ButanolHCID 198430Trimethylamine oxide dihydrateHCID 688081066,9-Dihydro-5H-6,9-methanocyclohepta[b]pyridine

Produkt 1

HCID 688083706,7,8,9-Tetrahydro-5H-6,9-methanocyclohepta[b]pyridine-7,8-diol

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 30318Osmium TetroxideKatalysator2×HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

3-Aza-tricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene (960 mg, 6.1 mmol) and trimethylamine N-oxide dihydrate (748 mg, 6.73 mmol) were stirred in dichloromethane (15 mL) and treated with osmium tetroxide (OsO4, 0.2 mL of a 15 mol % t-butanol solution) and the mixture was stirred vigorously. After 18 h, the residue was poured onto a silica gel column (2×6 inch) and eluted with hexanes (100 mL) then EtOAc to elute product as an oil that crystallizes on standing (1.16 g, 100%). (TLC EtOAc Rf 0.17); 1H NMR (400 MHz, CDCl3) δ 8.12 (d, J=4.9 Hz, 1H), 7.40 (d, J=7.5 Hz, 1H), 7.07 (dd, J=7.5, 4.9 Hz, 1H), 4.19 (d, J=6.0 Hz, 1H), 3.90 (d, J=6.0 Hz, 1H), 3.45 (s, 1H), 3.00 (dd, J=17.3, 4.8 Hz, 1H), 2.67 (d, J=17.3 Hz, 1H), 2.43 (m, 2H), 1.59 (d, J=11.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 159.4, 147.6, 138.1, 130.9, 122.3, 77.1, 75.4, 51.6, 42.2, 33.9, 28.5; APCl MS m/z 192.1 (M)+.

Aufarbeitung

  1. additionthe residue was poured onto a silica gel column (2×6 inch)
  2. washeluted with hexanes (100 mL)
  3. washEtOAc to elute product as an oil that
  4. customcrystallizes

Quellen und Nachweise

ORD-Eintrag
ord-cde964424edf458fa86a5b10c87795d9
Quelldatensatz
uspto-grants-2008_11
Patentnummer
US07456177B2

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