反応 #577232

反応方程式

N′-[3-(2,2-Di-tert-butyl-7-hydroxy-tetrahydro-furo[3,2-d][1,3,2]dioxasilin-6-yl)-2-oxo-2,3-dihydro-thiazolo[4,5-d]pyrimidin-5-yl]-N,N-dimethyl-formamidine

Isopropyl chloroformate

→

14

収率 51.0%

Carbonic acid 2,2-di-tert-butyl-6-[5-(dimethylamino-methyleneamino)-2-oxo-thiazolo[4,5-d]pyrimidin-3-yl]-tetrahydro-furo[3,2-d][1,3,2]dioxasilin-7-yl ester isopropyl ester

収率 51.0%

溶媒

DCM

反応条件

後処理

1. 1
   workup.ADDITIONaddition
2. 2
   濃縮then concentrated in vacuo

実験手順

N′-[3-(2,2-Di-tert-butyl-7-hydroxy-tetrahydro-furo[3,2-d][1,3,2]dioxasilin-6-yl)-2-oxo-2,3-dihydro-thiazolo[4,5-d]pyrimidin-5-yl]-N,N-dimethyl-formamidine (1.83 g, 3.68 mmol) was dissolved in DCM (18.4 mL) and DMAP (450 mg, 3.68 mmol) was added. Isopropyl chloroformate (7.37 mL, 1 M in toluene, 7.37 mmol) was added over 12 h via syringe pump. The reaction was stirred an additional 5 h following addition then concentrated in vacuo. The residue was submitted to flash chromatography (50-100% EtOAc-Hex) yielding 1.09 g (51%) of 14 as a white solid: 1H NMR (400 MHz, DMSO-d6) δ 8.61 (1H, s), 8.60 (1H, s), 6.27 (1H, t, J=7.4 Hz), 6.10 (1H, d, J=7.9 Hz), 5.06 (1H, t, J=6.9 Hz), 4.61 (1H, septet, J=6.1 Hz), 4.49 (1H, t, J=10.5 Hz), 4.30-4.36 (1H, m), 3.93 (1H, dd, J1=5.3 Hz, J2=10.8 Hz), 3.14 (3H, s), 3.03 (3H, s), 1.14 (3H, d, J=6.2 Hz), 1.04 (3H, d, J=5.4 Hz), 1.04 (3H, s), 1.00-1.03 (18H, m)8.61 (1H, s), 8.60 (1H, s), 6.27 (1H, t, J=7.4 Hz), 6.10 (1H, d, J=7.9 Hz), 5.06 (1H, t, J=6.9 Hz), 4.61 (1H, septet, J=6.1 Hz), 4.49 (1H, t, J=10.5 Hz), 4.30-4.36 (1H, m), 3.93 (1H, dd, J1=5.3 Hz, J2=10.8 Hz), 3.14 (3H, s), 3.03 (3H, s), 1.14 (3H, d, J=6.2 Hz), 1.04 (3H, d, J=5.4 Hz), 1.04 (3H, s), 1.00-1.03 (18H, m). [M+H]+ @ m/z 583.0.

出典