Water → (S)-N-[(2R,3S)-2-methyl-3-tetrahydropyranyloxybutylidene]-p-toluenesulfinamide

HRID 2113401Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2113401
[C:1]1([CH3:10])[CH:6]=[CH:5][C:4]([S@@:7]([NH2:9])=[O:8])=[CH:3][CH:2]=1.[CH3:11][C@@H:12]([C@@H:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=CC=1)[CH3:16])[CH:13]=O.[OH2:25]>ClCCl>[CH3:13][C@@H:12]([C@@H:15]([O:17][CH:18]1[CH2:19][CH2:24][CH2:23][CH2:22][O:25]1)[CH3:16])[CH:11]=[N:9][S@:7]([C:4]1[CH:5]=[CH:6][C:1]([CH3:10])=[CH:2][CH:3]=1)=[O:8]

Komponenten

5

Edukt 3

HCID 962WaterHCID 11116285(S)-4-methylbenzenesulfinamideHCID 86590269(2S,3S)-2-methyl-3-benzyloxybutyraldehyde

Produkt 1

HCID 69214407(S)-N-[(2R,3S)-2-methyl-3-tetrahydropyranyloxybutylidene]-p-toluenesulfinamideAusbeute 77 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Ti(OEt)4 (1.71 g, 1.57 ml, 7.5 mmol, 5 eq.) was added dropwise, at room temperature, to a mixture of (S)-(+)-p-toluenesulfinamide (233 mg, 1.50 mmol) and (2S,3S)-2-methyl-3-benzyloxybutyraldehyde (6) (280 mg, 1.50 mmol) in dichloromethane (25 ml). The solution was refluxed under argon for 5.5 hours. The reaction was neutralized at 0° C. adding water (25 ml). The cloudy solution was filtered on Celite and the filter cake was washed with dichloromethane (2×25 ml). The phases were separated, the aqueous phase was extracted with dichloromethane and the combined organic portions were dried over Na2SO4 and they were concentrated. Flash chromatography on a silica gel column (heptane/EtOAc=6:1) produced (S)-N-[(2R,3S)-2-methyl-3-tetrahydropyranyloxybutylidene]-p-toluenesulfinamide (7) (375 mg, 77%): IR (CHCl3) 3010, 2976, 2946, 2878, 2854, 1620, 1598, 1494, 1455, 1443, 1380, 1354, 1214 cm−1; 1H NMR (250 MHz, CDCl3) δ 8.31 (d, J=5.8 Hz, 0.5H); 8.23 (d, J=5.3 Hz, 0.5H); 7.55 (m, 2H); 7.29 (m, 2H); 4.79 to 4.70 (m, 0.5H); 4.55 to 4.51 (m, 0.5H); 4.00 to 3.82 (m, 1.5H); 3.77 to 3.70 (m, 0.5H); 3.48 to 3.41 (m, 1H); 2.84 to 2.64 (m, 1H); 2.39 (s, 3H); 1.78 to 1.41 (m, 6H); 1.25 (d, J=6.4 Hz, 1.5H); 1.14 (d, J=5.7 Hz, 3H); 1.14 (d, J=7.1 Hz, 1.5H); 1.09 (d, J=7.0 Hz, 1.5H); 13C NMR (75 MHz, CDCl3) δ 169.2; 168.6; 141.9; 141.8; 141.2; 129.4; 124.4; 124.2; 99.6; 94.6; 76.4; 72.2; 62.3; 61.8; 45.6; 45.2; 30.6; 30.5; 25.2; 25.2; 21.1; 19.4; 19.1; 18.9; 16.3; 13.0; 12.5; MS (CI) m/z 324 [M+H]+. HRMS: calculated for C17H26NO3S (M+H), 324.16333; found, 324.16141.

Aufarbeitung

  1. temperatureThe solution was refluxed under argon for 5.5 hours
  2. customwas neutralized at 0° C.
  3. filtrationThe cloudy solution was filtered on Celite
  4. washthe filter cake was washed with dichloromethane (2×25 ml)
  5. customThe phases were separated
  6. extractionthe aqueous phase was extracted with dichloromethane
  7. dry with materialthe combined organic portions were dried over Na2SO4 and they
  8. concentrationwere concentrated

Quellen und Nachweise

ORD-Eintrag
ord-089d717d7e6445e696dfdc6c45581bb7
Quelldatensatz
uspto-grants-2008_10
Patentnummer
US07432087B2

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