4,4,4-Trifluorobutan-2-one → (R)-2-methyl-N-(4,4,4-trifluorobutan-2-ylidene)propane-2-sulfinamide

To a solution of 4,4,4-trifluorobutan-2-one (12 g, 95 mmol) in THF (150 ml) was added titanium (IV) isopropoxide (42 ml, 142 mmol) and (R)-tert-butanesulfinamide (17.3 g, 142 mmol). The solution was heated to reflux for 22 h, cooled to RT, and poured into a vigorously-stirred brine solution. The mixture was filtered through a pad of Celite, the filter cake washed with EtOAc, and the filtrate separated. The aqueous layer was extracted with EtOAc, the organic layers combined and washed with brine, dried on Na2SO4, and concentrated in vacuo. The residue was purified by column chromatography (15% to 60% EtOAc in hexanes) to afford the title compound as a yellow oil (14.0 g, 65%). 1H NMR (CDCl3, 400 MHz) δ 1.25 (s, 9H), 2.45 (s, 3H), 3.19 (q, J=14.4 Hz, 2H). 19F NMR (CDCl3, 376 MHz) δ −61.03 (t, J=10.5 Hz), −62.8 (t, J=10.5 Hz).

1. temperatureThe solution was heated
2. temperatureto reflux for 22 h
3. filtrationThe mixture was filtered through a pad of Celite
4. washthe filter cake washed with EtOAc
5. customthe filtrate separated
6. extractionThe aqueous layer was extracted with EtOAc
7. washwashed with brine
8. customdried on Na2SO4
9. concentrationconcentrated in vacuo
10. customThe residue was purified by column chromatography (15% to 60% EtOAc in hexanes)

ORD record

ord-b980c11733b64b0fa9f81b02f79a5e99

Source dataset

uspto-grants-2014_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08729112B2