Trichloroacetonitrile → HCID 178476615, compound

HRID 62295Notes

Reaction equation

C1CCN2C(=NCCC2)CC1.[C:12]([O:15][C@@H:16]1[C@H:21]([O:22][C:23](=[O:25])[CH3:24])[C@@H:20]([O:26][C:27](=[O:29])[CH3:28])[C@H:19]([CH3:30])[O:18][C@H:17]1[O:31][C@@H:32]1[C@@H:38]([OH:39])[C@H:37]([CH3:40])[O:36][C@@:34]([C@H:41]2[O:70][C@H:69]([CH2:71][O:72][CH2:73][C:74]3[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=3)[C@@H:60]([O:61][CH2:62][C:63]3[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=3)[C@H:51]([O:52][CH2:53][C:54]3[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=3)[C@H:42]2[O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)([OH:35])[C@@H:33]1[O:80][C:81](=[O:88])[C:82]1[CH:87]=[CH:86][CH:85]=[CH:84][CH:83]=1)(=[O:14])[CH3:13].[Cl:89][C:90]([Cl:94])([Cl:93])[C:91]#[N:92]>C(Cl)Cl>[Cl:89][C:90]([Cl:94])([Cl:93])[C:91](=[NH:92])[OH:14].[C:12]([O:15][C@@H:16]1[C@H:21]([O:22][C:23](=[O:25])[CH3:24])[C@@H:20]([O:26][C:27](=[O:29])[CH3:28])[C@H:19]([CH3:30])[O:18][C@H:17]1[O:31][C@@H:32]1[C@@H:38]([OH:39])[C@H:37]([CH3:40])[O:36][C@@:34]([C@H:41]2[O:70][C@H:69]([CH2:71][O:72][CH2:73][C:74]3[CH:75]=[CH:76][CH:77]=[CH:78][CH:79]=3)[C@@H:60]([O:61][CH2:62][C:63]3[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=3)[C@H:51]([O:52][CH2:53][C:54]3[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=3)[C@H:42]2[O:43][CH2:44][C:45]2[CH:46]=[CH:47][CH:48]=[CH:49][CH:50]=2)([OH:35])[C@@H:33]1[O:80][C:81](=[O:88])[C:82]1[CH:87]=[CH:86][CH:85]=[CH:84][CH:83]=1)(=[O:14])[CH3:13]

Participants

Conditions

Temperature: 0 °C

Procedure

DBU (100 μL) was added at 0° C. to a solution of the hemiacetal 522 (3.8 g, 3.58 mmol) in DCM (40 mL) containing trichloroacetonitrile (4 mL). The mixture was stirred for 30 min at 0° C., and volatiles were evaporated. Flash chromatography (solvent B, 7:3+0.2% Et3N) of the crude material gave the donor 505 (3.9 g, 90%) as a while solid; 1H NMR (α anomer): δ 8.75 (s, 1H, NH), 8.13-7.12 (m, 25H, Ph), 6.40 (d, 1H, J1,2=2.4 Hz, H-1C), 5.54 (br s, 1H, H-2B), 5.49 (dd, 1H, J2,3=2.9 Hz, H-2C), 5.26 (d, 1H, J1,2=2.8 Hz, H-1E), 5.20 (dd, 1H, J2,3=J3,4=10.0 Hz, H-3B), 5.17 (br s, 1H, H-1B), 4.96 (dd, 1H, H-4B), 4.99-4.41 (m, 8H, OCH2), 4.34 (m, 1H, H-3C), 4.14-4.02 (m, 3H, H-3E, 5E, 5C), 3.87 (m, 1H, H-4C), 3.78 (dq, 1H, J4,5=9.5, J5,6=6.1 Hz, H-5B), 3.70 (m, 2H, H-6aE, 6bE), 3.65 (dd, 1H, J2,3=3.4, J3,4=9.8 Hz, H-2E), 3.57 (pt, 1H, J2,3=J3,4=9.4 Hz, H-4E), 1.86, 1.83 (2s, 9H, CH3CO), 1.42 (d, 3H, J5,6=6.2 Hz, H-2C), 0.98 (d, 3H, H-6B); 13C NMR (α anomer): δ 170.3, 170.1, 169.9, 166.1 (4C, C═O), 160.7 (C═NH), 139.2-127.8 (Ph), 100.2 (C-1B), 98.1 (C-1E), 94.8 (C-1C), 91.2 (CCl3), 82.4 (C-4C), 82.0 (C-3E), 81.2 (br s, C-2E), 78.5 (br s, C-3C), 78.3 (C-4E), 75.9, 75.4, 74.3, 73.3 (4C, CH2Ph), 71.8 (C-5E), 71.7 (C-2C), 71.3 (C-4B), 70.8 (br s, C-5C), 70.0 (C-2B), 69.3 (C-3B), 69.2 (C-6E), 67.6 (C-5B), 21.3, 21.0, 20.9 (3C, CH3CO), 18.9 (C-6C), 17.1 (C-6B). Anal. Calcd. for C61H66Cl3NO18: C, 60.67; H, 5.51; N, 1.16%. Found: C, 60.53; H, 5.48; N, 1.38%.

Workup

customvolatiles were evaporated

Sources & evidence

ORD record: ord-a3cd8338f71b49fcba00904b32eade44
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09446109B2

Reaction notes

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