Acetonitrile → 5'-O-Benzoyl-2',3'-didehydro-3'-deoxy-4'-ethynylthymidine

HRID 215729

Reaction equation

CC#N.[C:4]([O:12][CH2:13][C@@:14]1([C:33]#[CH:34])[O:18][C@@H:17]([N:19]2[CH:27]=[C:25]([CH3:26])[C:23](=[O:24])[NH:22][C:20]2=[O:21])[CH2:16][C@H:15]1OS(C)(=O)=O)(=[O:11])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C1CN2C(=NCCC2)C1>CC(O)=O>[C:4]([O:12][CH2:13][C@@:14]1([C:33]#[CH:34])[O:18][C@@H:17]([N:19]2[CH:27]=[C:25]([CH3:26])[C:23](=[O:24])[NH:22][C:20]2=[O:21])[CH:16]=[CH:15]1)(=[O:11])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To an CH3CN (4 mL) solution of 5 (101.9 mg, 0.18 mmol) was added DBN (67 μL, 0.54 mmol) at 0° C. under Ar atmosphere, and the mixture was stirred at 80° C. for 9 h. The reaction mixture was neutralized by adding AcOH, and partitioned between CHCl3/sat. aqueous NaHCO3. Silica gel column chromatography (1.5% MeOH in CH2Cl2) of the organic layer gave 6 (60 mg, 95%) as solid: 1H NMR (CDCl3) δ1.42 (3H, d, JMe,6=1.2 Hz, Me-5), 2.70 (1H, s, C□CH),), 4.59 (1H, d, J5′a,5′b=12.0 Hz, H-5′a), 4.76 (1H, d, J5′,5′b=12.0 Hz, H-5′b), 5.99 (1H, dd, J1′,2′=1.2, J2′,3′=5.9, H-2′), 6.38 (1H, dd, J1′,3′=2.0 and J2′,3′=5.9 Hz, H-3′), 6.98 (1H, d, JMe,6=1.2 Hz), 7.12 (1H, m, H-1′), 7.45-7.49, 7.60-7.63 and 8.00-8.03 (5H, each as m, Ph), 8.37 (1H, br); FAB-MS (m/z) 353 (M++H).

Workup

custompartitioned between CHCl3/

Sources & evidence

ORD record: ord-7695b948fb364e509d3eba3ccfaa76d5
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08193165B2

Linked notes

Loading…