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

HRID 18255

反応式

HRID 18255 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][CH2:9][C:10]([O:12][CH3:13])=[O:11])=[N:6][CH:7]=1.[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:17])[CH:15]=[CH2:16].CCN(C(C)C)C(C)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)CC.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:13][O:12][C:10]([CH2:9][NH:8][C:5]1[N:6]=[CH:7][C:2](/[CH:16]=[CH:15]/[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:3][CH:4]=1)=[O:11]

参加物

7

反応物 4

HCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 22139049Methyl 2-((5-bromopyridin-2-yl)amino)acetate

生成物 1

HCID 66905699tert-butyl (E)-3-[6-[N-(methoxycarbonylmethyl)amino]pyridin-3-yl]acrylate収率 93.3%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 7854Propionitrile溶媒

実験手順

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).

後処理

  1. temperaturewas heated
  2. temperatureat reflux
  3. concentrationthen was concentrated to dryness
  4. customThe residue was purified by flash chromatography on silica gel (40% EtOAc/hexane)

出典と根拠

ORDレコード
ord-765f834566c84bcfa82e57d0ee0a57e4
出典データセット
uspto-grants-2010_06
特許番号
US07741339B2

関連ノート

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