(Dimethyl sulfide)trihydroboron → Ethyl 5-oxa-6-azaspiro[3.4]octane-7-carboxylate

HRID 1185941Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1185941
[CH2:1]([O:3][C:4]([C:6]1[CH2:13][C:9]2([CH2:12][CH2:11][CH2:10]2)[O:8][N:7]=1)=[O:5])[CH3:2].CSC.B>O1CCCC1>[CH2:1]([O:3][C:4]([CH:6]1[CH2:13][C:9]2([CH2:10][CH2:11][CH2:12]2)[O:8][NH:7]1)=[O:5])[CH3:2]

Komponenten

4

Edukt 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 59611573Ethyl 5-oxa-6-azaspiro[3.4]oct-6-ene-7-carboxylate

Produkt 1

HCID 59611538Ethyl 5-oxa-6-azaspiro[3.4]octane-7-carboxylateAusbeute 29 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of crude 5-oxa-6-aza-spiro[3.4]oct-6-ene-7-carboxylic acid ethyl ester (7.5 g, <40.9 mmol) in tetrahydrofuran (270 mL) at 0° C. was slowly added a solution of borane-dimethyl sulfide complex (10 M in THF, 16.4 mL, 164 mmol). The reaction was allowed to warm to room temperature overnight then recooled to 0° C., and quenched by the careful addition of water. The mixture was diluted with ethyl acetate, washed with water and brine, dried (MgSO4), and concentrated to yield a large amount of white solids. These solids were thoroughly triturated three times with dichloromethane (150 mL). The combined dichloromethane washings were concentrated and the resulting oil was purified by flash chromatography to yield 5-oxa-6-aza-spiro[3.4]octane-7-carboxylic acid ethyl ester (1.08 g, 29% over 2 steps). 1H-NMR: 400 MHz, (CDCl3) δ: 8.01-7.95 (br, 1H), 4.39-4.28 (m, 2H), 4.18-4.10 (m, 1H), 2.80-2.75 (m, 1H), 2.62-2.49 (m, 2H), 2.37-2.29 (m, 1H), 2.25-2.17 (m, 1H), 2.13-1.95 (m, 1H), 1.88-1.79 (m, 1H), 1.68-1.56 (m, 1H), 1.34 (t, J=7.1 Hz, 3H) ppm.

Aufarbeitung

  1. customthen recooled to 0° C.
  2. customquenched by the careful addition of water
  3. additionThe mixture was diluted with ethyl acetate
  4. washwashed with water and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customto yield a large amount of white solids
  8. customThese solids were thoroughly triturated three times with dichloromethane (150 mL)
  9. concentrationThe combined dichloromethane washings were concentrated
  10. customthe resulting oil was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-21d0ab73ed244e65a6bef0b12a69e5d0
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08669234B2

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