Pyridine → HCID 86658277, 화합물

HRID 74839노트

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HRID 74839 반응식
[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

참가 물질

8

반응물 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

생성물 1

HCID 86658277HCID 86658277, 화합물수율 60%

시약·촉매·용매 2

HCID 6344Dichloromethane용매2회HCID 8471Triethylamine용매

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온도
0 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-f488dd4163d54d7e958e7cbf9d3fb91c
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08828952B2

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