Water → HCID 87383933, compound

HRID 588486Notes

Reaction equation

[CH3:1][C:2]([S@@:5]([NH2:7])=[O:6])([CH3:4])[CH3:3].[CH:8]([C:10]1[S:14][C:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:12][CH:11]=1)=O.O>C(Cl)Cl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[C:2]([S@@:5](/[N:7]=[CH:8]/[C:10]1[S:14][C:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:12][CH:11]=1)=[O:6])([CH3:4])([CH3:3])[CH3:1]

Participants

Conditions

Temperature: 0 °C

Procedure

To a 500-mL round-bottom flask was added (S)-(−)-2-methyl-2-propanesulfinamide (1.62 g, 13.4 mmol), and tert-butyl 5-formylthiophene-2-carboxylate (2.37 g, 11.2 mmol), and DCM (100 mL). The mixture was cooled to 0° C., then titanium tetraisopropoxide (19.8 mL, 67.0 mmol) was added. After the solution was warmed to rt and stirred for 16 h, the reaction mixture was diluted with DCM (200 mL). To the flask was added water (19.8 mL) slowly. The mixture was vigorously stirred at rt for 30 min, then filtered through a pad of Celite. The filtrate was concentrated to give a solid. Purification via flash chromatography (hexanes to 10% EtOAc-hexanes) afforded (S,E)-tert-butyl 5-((tert-butylsulfinylimino)methyl)thiophene-2-carboxylate (3.07 g, 87%) as a white solid. 1H NMR (CDCl3, 400 MHz) δ 8.65 (s, 1H), 7.72 (d, J=4.0 Hz, 1H), 7.65 (d, J=3.8 Hz, 1H), 1.58 (s, 9H), 1.24 (s, 9H).

Workup

temperatureAfter the solution was warmed to rt
stirringThe mixture was vigorously stirred at rt for 30 min
filtrationfiltered through a pad of Celite
concentrationThe filtrate was concentrated
customto give a solid
customPurification via flash chromatography (hexanes to 10% EtOAc-hexanes)

Sources & evidence

ORD record: ord-ef62e2aa7db9456ba2043f7f7f36847f
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09227951B2

Reaction notes

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