Water → (2R,3S,4S,5R,6S)-3,4,5-tris(Benzyloxy)-2-((benzyloxy)methyl)-6-(p-tolylthio)tetrahydro-2H-pyran

HRID 1862755ノート

反応式

HRID 1862755 の反応式
[S:1]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)[C@@H:2]1[O:10][C@H:9]([CH2:11][OH:12])[C@H:7]([OH:8])[C@H:5]([OH:6])[C@H:3]1[OH:4].[H-].[Na+].[CH:22]1[CH:27]=[CH:26][C:25]([CH2:28]Br)=[CH:24][CH:23]=1.O>CN(C=O)C>[CH2:28]([O:4][C@@H:3]1[C@@H:5]([O:6][CH2:28][C:25]2[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=2)[C@@H:7]([O:8][CH2:28][C:25]2[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=2)[C@@H:9]([CH2:11][O:12][CH2:19][C:16]2[CH:17]=[CH:18][CH:13]=[CH:14][CH:15]=2)[O:10][C@H:2]1[S:1][C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)[C:25]1[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=1

参加物

6

反応物 4

HCID 962WaterHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 7315241(2R,3R,4S,5R,6S)-2-(Hydroxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triol

生成物 1

HCID 11050551(2R,3S,4S,5R,6S)-3,4,5-tris(Benzyloxy)-2-((benzyloxy)methyl)-6-(p-tolylthio)tetrahydro-2H-pyran収率 177.6%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
-10 °C

実験手順

p-Methylphenyl 1-thio-β-D-galactopyranoside (1.0 g, 3.5 mmol) was dissolved in dry DMF (15 mL) and cooled to −10° C. At this temperature (840 mg, 35 mmol) NaH was added and the mixture allowed to warm up to rt. and stirred for an additional 10 min. Then BnBr (4.1 mL, 35 mmol) was added, and the mixture was stirred for 5 h. At 0° C. 10 mL H2O was added and the mixture extracted with EtOAc (3×50 mL). The organic layer was dried over MgSO4 and evaporated to dryness. Flash chromatography using Hexane/EtOAc (5:1) gave the title compound as a white solid (2.01 g, 89%). [α]D22 −1.2° (c, 0.5, CHCl3); 1H-NMR (400 MHz, CDCl3), δ 2.27 (s, 3H), 3.56-3.65 (m, 4H), 3.89 (t, 1H, J=9.4 Hz) 3.97 (s, 1H), 4.42 (ABq, 2H, J=11.6 Hz), 4.59-4.60 (m, 3H), 4.70 (m, 3H), 4.73 (ABq, 2H, J=10.1 Hz), 4.95 (d, 1H, J=11.5 Hz), 6.98 (d, 2H, J=8.6 Hz), 7.25-7.47 (m, 22H); 13C-NMR (400 MHz, CDCl3), δ 21.04, 68.68, 72.63, 73.48, 74.34, 75.54, 77.16, 77.24, 84.13, 87.95, 127.36, 127.49, 127.60, 127.65, 127.71, 127.78, 127.86, 128.09, 128.26, 128.35, 129.49, 132.10; HRMS (M+Cs) calcd for C41H42O5SCs 779.1807, found 779.1782.

後処理

  1. temperatureto warm up to rt
  2. stirringthe mixture was stirred for 5 h
  3. customAt 0° C
  4. extractionthe mixture extracted with EtOAc (3×50 mL)
  5. dry with materialThe organic layer was dried over MgSO4
  6. customevaporated to dryness

出典と根拠

ORDレコード
ord-8e78458061604b85842c1ee98e423378
出典データセット
uspto-grants-2003_03
特許番号
US06538117B1

反応ノート

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