Trichloroacetonitrile → HCID 131729468, compound

HRID 62290Notes

Reaction equation

[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[O:8][C@@H:7]([O:20][C@@H:21]2[C@H:27]([O:28][CH2:29][C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C@@H:26]([O:36][CH2:37][C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)[C@H:25]([CH3:44])[O:24][C@H:22]2[OH:23])[C@@H:6]1[NH:45][C:46](=[O:51])[C:47]([Cl:50])([Cl:49])[Cl:48])(=[O:3])[CH3:2].[Cl:52][C:53]([Cl:57])([Cl:56])[C:54]#[N:55].C1CCN2C(=NCCC2)CC1>C(Cl)Cl>[Cl:52][C:53]([Cl:57])([Cl:56])[C:54]([O:23][C@@H:22]1[O:24][C@@H:25]([CH3:44])[C@H:26]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@H:21]1[O:20][C@@H:7]1[O:8][C@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:5]([O:4][C:1](=[O:3])[CH3:2])[C@H:6]1[NH:45][C:46](=[O:51])[C:47]([Cl:50])([Cl:49])[Cl:48])=[NH:55]

Participants

Conditions

Temperature: 0 °C

Procedure

The hemiacetal 318 (539 mg, 0.68 mmol) was dissolved in CH2Cl2 (50 mL), placed under argon and cooled to 0° C. Trichloroacetonitrile (0.6 mL, 6.8 mmol), then DBU (10 μL, 70 μmol) were added. The mixture was stirred at 0° C. for 30 min. The mixture was concentrated and toluene was co-evaporated from the residue. The residue was eluted from a column of silica gel with 7:3 cyclohexane-EtOAc and 0.2% of Et3N to give 306 (498 mg, 78%) as a colourless foam; [α]D−18° (c 1, CHCl3). 1H NMR: δ 8.48 (s, 1H, NH), 7.40-7.15 (m, 10H, Ph), 6.75 (d, 1H, J2,NH=8.5 Hz, NHD), 6.18 (d, 1H, J1,2=1.1 Hz, H-1A), 5.15 (pt, 1H, J2,3=J3,4=9.5 Hz, H-3D), 5.07 (pt, 1H, J4,5=9.5 Hz, H-4D), 4.82-4.50 (m, 4H, CH2Ph), 4.62 (d, 1H, J1,2=8.5 Hz, H-1D), 4.20-4.03 (m, 2H, J5,6=4.5, J6a,6b=12.3 Hz, H-6aD, 6bD), 3.98 (m, 1H, H-2D), 3.85 (dq, 1H, J4,5=9.5, J5,6=6.2 Hz, H-5A), 3.84 (dd, 1H, J2,3=3.3 Hz, H-2A), 3.83 (dd, 1H, J3,4=9.5 Hz, H-3A), 3.55 (m, 1H, H-5D), 3.45 (pt, 1H, H-4A), 1.98, 1.96, 1.93 (3s, 9H, OAc), 1.23 (d, 3H, H-6A); 13C NMR: δ 171.1, 170.0, 169.6, 162.1 (C═O), 138.4-127.2 (Ph), 101.7 (C-1D), 97.2 (C-1A), 92.6 (CCl3), 80.5 (C-4A), 79.1 (C-3A), 76.2 (C-2A), 76.2, 74.1 (2C, CH2Ph), 74.4 (C-3D), 74.1 (C-5D), 71.3 (C-5A), 68.6 (C-4D), 62.3 (C-6D), 56.3 (C-2D), 21.1, 21.0, 20.9 (3C, OAc), 18.2 (C-6A). Anal. Calcd for C36H40Cl6N2O13: C, 46.93; H, 4.38; N, 3.04%. Found: C, 46.93; H, 4.52; N, 2.85%.

Workup

concentrationThe mixture was concentrated
washThe residue was eluted from a column of silica gel with 7:3 cyclohexane-EtOAc and 0.2% of Et3N

Sources & evidence

ORD record: ord-59e450a682c7404e99a9fa7a6bfd8ba3
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09446109B2

Reaction notes

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