Dimethylformamide → 1-{[(4S)-2,2-Dimethyl-1,3-dioxolan-4-yl]methyl}-4-iodo-1H-pyrazole

HRID 2279724Notes

Reaction equation

[I:1][C:2]1[CH:3]=[N:4][NH:5][CH:6]=1.C1(C)C=CC(S(O[CH2:17][C@H:18]2[CH2:22][O:21][C:20]([CH3:24])([CH3:23])[O:19]2)(=O)=O)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].CN(C=O)C>CCOC(C)=O>[CH3:23][C:20]1([CH3:24])[O:19][C@@H:18]([CH2:17][N:4]2[CH:3]=[C:2]([I:1])[CH:6]=[N:5]2)[CH2:22][O:21]1

Participants

Conditions

Temperature: 100 °C

Procedure

A mixture of 4-iodopyrazole (1.40 g, 7.21 mmol), (R)-(−)-(2,2-dimethyl-1,3-dioxolan-4-yl)methyl p-toluenesulfonate (2.27 g, 7.93 mmol), Cs2CO3 (3.52 g, 10.8 mmol) and DMF (10 mL, 100 mmol) was heated to 100° C. for 16 hrs. The reaction mixture was diluted with EtOAc, washed with water (2×), dried with sodium sulfate, filtered and concentrated in vacuo to a solid which was purified using a Teledyne ISCO Combiflash® Rf system [0→20% EtOAc/Heptane] to afford 2.13 g of the title compound (96%). 1H NMR (400 MHz, CDCl3) d 7.55 (s, 1H), 7.52 (s, 1H), 4.43 (dd, J=4.8, 6.1 Hz, 1H), 4.24-4.28 (m, 2H), 4.08 (dd, J=6.3, 8.8 Hz, 1H), 3.76 (dd, J=6.1, 8.6 Hz, 1H), 1.39 (s, 3H), 1.34-1.37 (m, 3H). MS (ESI): m/z 309.01 [M+H]+. UPLC: tR=1.26 min (UPLC-TOF: polar—3 min).

Workup

washwashed with water (2×)
dry with materialdried with sodium sulfate
filtrationfiltered
concentrationconcentrated in vacuo to a solid which
customwas purified

Sources & evidence

ORD record: ord-3a90eae42d66473cb4d729dd3fed2fdf
Source dataset: uspto-grants-2015_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09133224B2

Reaction notes

Loading…