Pyridine → HCID 86658277、化合物

HRID 74839ノート

反応式

HRID 74839 の反応式
[C:1]([O:9][C@H:10]1[C@@H:15]([OH:16])[C@H:14]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@@H:13]([CH2:26][O:27][C:28](=[O:35])[C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[O:12][C@@H:11]1[O:36][C@H:37]1[C@H:50]([O:51][C:52](=[O:59])[C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)[C@@H:49]([CH2:60][O:61][C:62](=[O:69])[C:63]2[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=2)[O:48][C@H:39]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[C@H:38]1[O:70][C:71](=[O:78])[C:72]1[CH:77]=[CH:76][CH:75]=[CH:74][CH:73]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC(Cl)(Cl)C(=N)O[C@H:83]1[O:115][C@H:114]([CH2:116][O:117][C:118](=[O:125])[C:119]2[CH:124]=[CH:123][CH:122]=[CH:121][CH:120]=2)[C@@H:104]([O:105][C:106](=[O:113])[C:107]2[CH:112]=[CH:111][CH:110]=[CH:109][CH:108]=2)[C@H:94]([O:95][C:96](=[O:103])[C:97]2[CH:102]=[CH:101][CH:100]=[CH:99][CH:98]=2)[C@@H:84]1[O:85][C:86](=[O:93])[C:87]1[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=1.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C.N1C=CC=CC=1.C(Cl)(=O)C1C=CC=CC=1>C(Cl)Cl.CCN(CC)CC>[C:86]([O:85][C@H:84]1[C@@H:94]([O:95][C:96](=[O:103])[C:97]2[CH:102]=[CH:101][CH:100]=[CH:99][CH:98]=2)[C@H:104]([O:105][C:106](=[O:113])[C:107]2[CH:108]=[CH:109][CH:110]=[CH:111][CH:112]=2)[C@@H:114]([CH2:116][O:117][C:118](=[O:125])[C:119]2[CH:120]=[CH:121][CH:122]=[CH:123][CH:124]=2)[O:115][C@@H:83]1[O:16][C@H:15]1[C@H:14]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@@H:13]([CH2:26][O:27][C:28](=[O:35])[C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[O:12][C@H:11]([O:36][C@H:37]2[C@H:50]([O:51][C:52](=[O:59])[C:53]3[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=3)[C@@H:49]([CH2:60][O:61][C:62](=[O:69])[C:63]3[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=3)[O:48][C@H:39]([O:40][CH2:41][C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=3)[C@H:38]2[O:70][C:71](=[O:78])[C:72]2[CH:73]=[CH:74][CH:75]=[CH:76][CH:77]=2)[C@H:10]1[O:9][C:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)(=[O:93])[C:87]1[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=1

参加物

8

反応物 5

HCID 1049PyridineHCID 7412Benzoyl chlorideHCID 65367Trimethylsilyl triflateHCID 10963703alpha-D-Mannopyranose, 2,3,4,6-tetrabenzoate 1-(2,2,2-trichloroethanimidate)HCID 86658275Benzyl 2,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1->3)-2,4,6-tri-O-benzoyl-alpha-D-mannopyranoside

生成物 1

HCID 86658277HCID 86658277、化合物収率 60%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 8471Triethylamine溶媒

反応条件

温度
0 °C

実験手順

A solution of the alcohol 50 (424 mg, 0.401 mmol) and 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (357 mg, 0.481 mmol, 1.2 eq) in anhydrous DCM (7.5 mL) was stirred with powdered molecular sieves 3 Å (50 mg) at 0° C. for 1 h. A solution of TMSOTf (15 μL, 0.0802 mmol, 0.2 eq) in DCM (0.5 mL) was added dropwise via a syringe. The mixture was stirred at 0° C. for 2 h and TLC indicated complete conversion. Et3N (100 μL) was added. Pyridine (65 μL, 0.802 mmol) and benzoyl chloride (47 μL, 0.401 mmol) were added. The mixture was stirred at room temperature o/n and evaporated onto silica gel. Purification by column chromatography (silica 2.5×17 cm, gradient elution with hexane-EtOAc 210:30, 200:50, 180:60, 160:80 and 150:100) gave the trisaccharide 51 as a colourless gum (392 mg, 60%). 1H NMR (CDCl3, 400 MHz) δ 8.19-7.89 (m, 16H, Ph), 7.68-7.63 (m, 4H, Ph), 7.61-7.15 (m, 35H, Ph), 6.00 (dd or t, 1H, JH3-H4=10.7, JH4-H5=9.8, H4), 5.98 (dd or t, 1H, JH3-H4=9.8, J=9.8, H4), 5.92 (dd or t, 1H, J=10.7, J=9.8, H4), 5.72 (dd, 1H, JH1-H2=2.0, JH2-H3=3.9, H2), 5.56 (dd, 1H, JH2-H3=2.9, H3), 5.33 (d, 1H, J=2.0, H1), 5.26 (dd, 1H, J=2.0, H2), 5.19 (d, 1H, J=2.0, J=3.9, H2), 5.16 (d, 1H, J=2.0, H1), 4.90 (d, 1H, H1), 4.78 and 4.62 (AB quartet, 2H, Jgem=11.7, CH2), 4.65-4.56 (m, 3H), 4.45 (dd, 1H, Jgem=12.7, JH5-H6=3.9, H6), 4.35 (dd, 1H, H3), 4.34-4.28 (m, 2H), 4.24 (dd, 1H, J=12.7, JH5-H6=2.9, H6), 4.10 (dt or dm, 1H, H5), 4.01 (dd, 1H, J=12.7, H6), 3.95 (dd, 1H, JH5-H6=2.0, H6).

後処理

  1. stirringThe mixture was stirred at room temperature o/n and
  2. customevaporated onto silica gel
  3. customPurification
  4. washby column chromatography (silica 2.5×17 cm, gradient elution with hexane-EtOAc 210:30, 200:50, 180:60, 160:80 and 150:100)

出典と根拠

ORDレコード
ord-f488dd4163d54d7e958e7cbf9d3fb91c
出典データセット
uspto-grants-2014_09
特許番号
US08828952B2

反応ノート

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