1-(1-Naphthyl)-2-naphthol → (1,1'-Biphenyl)-2,2'-diol

HRID 14417

反応式

HRID 14417 の反応式
[P:1]([NH2:4])([O-:3])[O-:2].[C:5]1([C:16]2[C:25]3[C:20](=CC=CC=3)[CH:19]=[CH:18][CH:17]=2)[C:6]([OH:15])=[CH:7][CH:8]=[C:9]2[C:14]=1C=CC=C2>>[P:1]([NH2:4])([O-:3])[O-:2].[C:25]1([OH:2])[C:16]([C:5]2[C:6]([OH:15])=[CH:7][CH:8]=[CH:9][CH:14]=2)=[CH:17][CH:18]=[CH:19][CH:20]=1

参加物

4

反応物 2

HCID 27552601-(1-Naphthyl)-2-naphthol2 回HCID 10080320Phosphoramidite2 回

生成物 2

HCID 15731(1,1'-Biphenyl)-2,2'-diolHCID 10080320Phosphoramidite

実験手順

As shown in Table 1, the reaction proceeded smoothly at room temperature in the presence of [Ir(cod)Cl]2 (1 mol %) and phosphoramidite ligand 1 above (2 mol %, L/Ir=1) to give after 10 h branched product 3 in 84% isolated yield with excellent regioselectivity (3/4/5=98/1/1) and 95% enantiomeric excess (entry 1). Reaction at 50° C. for 4 h gave 89% of product 3 with 94% ee (entry 2). Reactions catalyzed by complexes of the diastereomeric form of phosphoramidite ligand L1 with opposite relative configuration of the binaphthol and amine unit were slow, even at 50° C., and formed the opposite enantiomer in 66% yield and 75% ee (entry 3). Complexes of binaphthol-derived ligands with achiral and smaller substituents at nitrogen (e.g., phosphoramidite ligand L3) produced lower ee's than did those of phosphoramidite ligand L1 (entry 4). Phosphoramidite ligand L2 with a biphenol unit gave product with a lower, though substantial enantioselectivity of 87% (entry 5).

後処理

  1. customwere slow, even at 50° C.
  2. customformed the opposite enantiomer in 66% yield and 75% ee (entry 3)
  3. customproduced lower ee's

出典と根拠

ORDレコード
ord-7499bcd78e4f4f5c80b6634575479b6c
出典データセット
uspto-grants-2010_06
特許番号
US07732365B2

関連ノート

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