Réaction #46533

Équation de réaction

5-bromo-2-(methoxycarbonylmethyl)aminopyridine

tert-butyl acrylate

DIEA

P(o-tol)3

→

title compound

Rendement 93.3%

tert-Butyl (E)-3-[6-[N-(methoxycarbonylmethyl)amino]pyridin-3-yl]acrylate

Rendement 93.3%

Solvants

propionitrile

Conditions de réaction

Traitement

1. 1
   Températurewas heated
2. 2
   Températureat reflux
3. 3
   Concentrationthen was concentrated to dryness
4. 4
   AutreThe residue was purified by flash chromatography on silica gel (40% EtOAc/hexane)

Mode opératoire

A solution of 5-bromo-2-(methoxycarbonylmethyl)aminopyridine (4.69 g, 19.1 mmole, from Preparation 28 (c)), tert-butyl acrylate (11.2 mL, 76.5 mmole), DIEA (6.7 mL, 38.5 mmole), Pd(OAc)2 (215 mg, 1 mmole), and P(o-tol)3 (583 mg, 2 mmole) in propionitrile (100 mL) was purged with Ar, then was heated at reflux. After 18 h, the reaction was allowed to cool to room temperature then was concentrated to dryness. The residue was purified by flash chromatography on silica gel (40% EtOAc/hexane) to give the title compound (5.21 g, 93%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 8.19 (s, 1 H), 7.62 (dd, 1 H), 7.47 (d, J=16.0 Hz, 1 H), 6.48 (d, J=8.7 Hz, 1 H), 6.17 (d, J=15.9 Hz, 1 H), 5.21 (br s, 1 H), 4.20 (d, J=5.4 Hz, 2 H), 3.79 (s, 3 H), 1.52 (s, 1 H).

Source