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

HRID 2113401ノート

反応式

HRID 2113401 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-089d717d7e6445e696dfdc6c45581bb7
出典データセット
uspto-grants-2008_10
特許番号
US07432087B2

反応ノート

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