Triethylamine → HCID 86613970, compound

HRID 1920707Notes

Reaction equation

ClC(Cl)(Cl)C(=N)O[C@H:5]1[O:32][C@H:31]([CH2:33][O:34][C:35](=[O:42])[C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C@@H:21]([O:22][C:23](=[O:30])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@H:16]([O:17][CH2:18][CH:19]=[CH2:20])[C@@H:6]1[O:7][C:8](=[O:15])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[CH2:46]([O:53][C@H:54]1[C@H:67]([O:68][CH2:69][C:70]2[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=2)[C@@H:66]([CH2:76][O:77][CH2:78][C:79]2[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=2)[O:65][C@H:56]([O:57][CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[C@H:55]1[OH:85])[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C.CCN(CC)CC>ClCCCl>[CH2:18]([O:17][C@H:16]1[C@H:21]([O:22][C:23](=[O:30])[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C@@H:31]([CH2:33][O:34][C:35](=[O:42])[C:36]2[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=2)[O:32][C@H:5]([O:85][C@H:55]2[C@@H:54]([O:53][CH2:46][C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[C@H:67]([O:68][CH2:69][C:70]3[CH:71]=[CH:72][CH:73]=[CH:74][CH:75]=3)[C@@H:66]([CH2:76][O:77][CH2:78][C:79]3[CH:80]=[CH:81][CH:82]=[CH:83][CH:84]=3)[O:65][C@@H:56]2[O:57][CH2:58][C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[C@H:6]1[O:7][C:8](=[O:15])[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)[CH:19]=[CH2:20]

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate [26] (902 mg, 1.21 mmol) and benzyl 3,4,6-tri-O-benzyl-α-D-mannopyranoside [27] (723 mg, 1.34 mmol) in 1,2-DCE (10 mL), was stirred in the presence of mol. sieves (1.0 g of 3 Å powder) under an atmosphere of argon (30 min). The mixture was cooled (0° C.) with continued stirring (10 min) prior to the addition of TMSOTf (219 μL, 1.21 mmol). After some time (10 min), Et3N (100 μL) was introduced and the mixture was filtered. The solvent was evaporated and the residue subjected to FC (10-50% EtOAc/hexane) to yield the tribenzoate (24) as, a colourless oil (1.14 g, 84%). 1H NMR (CDCl3) δ 3.67-3.81, 3.88-3.95, 4.06-4.15, 4.30-4.35 (4 m, 12 H; H-2I,-3I,-4I,-5I,-6aII,-6bII,-3II,-5II,-6aII,-6bII, OCH2), 4.94-4.70 (m, 7 H; CH2Ph), 4.84 (d, 1 H, JA,B 10.8 Hz; A of AB quartet), 4.93-4.96, 5.04-5.09 (2 m, 2 H; ═CH2), 5.02 (d, 1 H, J1,2 1.9 Hz; H-1I), 5.24 (d, 1 H; J1,2 1.9 Ha; H-1II), 5.59-5.69 (m, 1 H; ═CH), 5.72 (dd, 1 H, J2,3 3.1 Hz; H-2II), 5.75 (dd, 1H, J3,4 9.8, J4,5 9.9 Hz; H-4II), 7.09-7.58, 7.97-8.06 (2 m, 35 H; Ar). 13C NMR (CDCl3) δ 61.50, 63.49 (2C; C-6I,-6II), 68.63, 69.17, 69.31, 69.46, 69.64, 71.08, 72.04, 72.64, 73.60, 74.73, 75.30, 75.38 (13C; C-3I,-4I,-5I,-2II,-3II,-4II,-5II, OCH2, CH2Ph), 79.97 (C-2I), 98.52, 99.60 (C-1I,-1II), 117.67 (═CH2), 127.70-138.43 (43C; ═CH, Ar), 165.61, 165.69, 166.42 (3C; C═O).

Workup

customunder an atmosphere of argon (30 min)
stirringwith continued stirring (10 min)
filtrationthe mixture was filtered
customThe solvent was evaporated

Sources & evidence

ORD record: ord-ffde79b803da4482ad9cdc4ab0ec2e6f
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08173606B2

Reaction notes

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