Hydroxylamine → 4-(tert-Butyl-dimethyl-silanyloxymethyl)-3-methyl-pyridin-2-ylamine

Participants

Reaction Conditions

Reaction Steps

An oven dried flask under N2 was charged with 4-(tert-butyl-dimethyl-silanyloxymethyl)-2-chloro-3-methyl-pyridine (10-1, 1.00 g, 3.68 mmol), NaOtBu (0.495 g, 5.15 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.067 g, 0.070 mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.137 g, 0.22 mmol) and anhydrous toluene (10 mL). Benzophenone imine (0.740 mL, 4.41 mmol) was added and the reaction was heated to 80° C. After 3 hours the reaction was allowed to cool to room temperature and was diluted with 50 mL of diethyl ether. The resulting mixture was filtered through celite, washing with ether. The filtrate was concentrated, redissolved in 10 mL MeOH and hydroxylamine (50% aqueous, 0.676 mL, 11.0 mmol) was added. After stirring overnight, an additional 0.680 mL of hydroxylamine solution was added. After 8 hours the solution was concentrated in vacuo. The residue was purified by flash column chromatography (sample was loaded in DCM and eluted with a DCM to 9:1 DCM/MeOH gradient) to afford the title product. 1H NMR indicates that product is contaminated with BINAP dioxide. 1H NMR (CDCl3) δ 7.80 (d, 1H), 6.85 (d, 1H), 4.65 (s, 2H), 4.35 (bs, 2H), 2.00 (s, 3H), 0.95 (s, 9H), 0.15 (s, 6H).

Provenance & Evidence