Water → tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 1473358ノート

反応式

HRID 1473358 の反応式
CC1(C)C(C)(C)OB([C:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:11][CH:10]=2)O1.[Br:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]([F:33])([F:32])[F:31])=[CH:26][C:25]=1I.P([O-])([O-])([O-])=O.[K+].[K+].[K+].O>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[Br:23][C:24]1[CH:25]=[CH:26][C:27]([C:30]([F:31])([F:32])[F:33])=[CH:28][C:29]=1[C:9]1[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16])[CH2:11][CH:10]=1

参加物

7

反応物 4

HCID 962WaterHCID 62657Potassium Phosphate, TribasicHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 467352311-Bromo-2-iodo-4-(trifluoromethyl)benzene

生成物 1

HCID 71259576tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate収率 70%

試薬・触媒・溶媒 2

HCID 178418807HCID 178418807、化合物触媒HCID 312751,4-Dioxane溶媒

実験手順

A solution of PdCl2(dppf)-CH2Cl2 adduct (0.582 g, 0.712 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (4.63 g, 14.96 mmol), 1-bromo-2-iodo-4-(trifluoromethyl)benzene (2.298 ml, 14.25 mmol), and potassium phosphate (9.07 g, 42.7 mmol) in 50 mL dioxane/25 mL water was heated to 80° C. for 2 hours. LC/MS showed mostly product, so the reaction mixture was poured into water and was extracted with DCM. The organics were dried over MgSO4 and concentrated. Purification of the crude residue by silica gel column chromatography (0-30% EtOAc/heptane) gave tert-butyl 4-(2-bromo-5-(trifluoromethyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate (4.05 g, 9.97 mmol, 70.0% yield) as a clear oil. m/z (ESI) 430.2 (M+Na)+.

後処理

  1. extractionwas extracted with DCM
  2. dry with materialThe organics were dried over MgSO4
  3. concentrationconcentrated
  4. customPurification of the crude residue by silica gel column chromatography (0-30% EtOAc/heptane)

出典と根拠

ORDレコード
ord-19f4a83ccba84ffa8ac75a856fe90f59
出典データセット
uspto-grants-2015_04
特許番号
US09012443B2

反応ノート

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