4-Nitrobenzoic Acid → (6S,9R)-6-(2,3-difluorophenyl)-6-hydroxy-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-9-yl 4-nitrobenzoate

HRID 1879373ノート

反応式

HRID 1879373 の反応式
[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C@:9]1([OH:21])[CH2:19][CH2:18][C@H:17]([OH:20])[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:11]2[CH2:10]1.[N+:22]([C:25]1[CH:33]=[CH:32][C:28]([C:29](O)=[O:30])=[CH:27][CH:26]=1)([O-:24])=[O:23].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[N+:22]([C:25]1[CH:26]=[CH:27][C:28]([C:29]([O:20][C@H:17]2[C:12]3=[N:13][CH:14]=[CH:15][CH:16]=[C:11]3[CH2:10][C@@:9]([C:3]3[CH:4]=[CH:5][CH:6]=[C:7]([F:8])[C:2]=3[F:1])([OH:21])[CH2:19][CH2:18]2)=[O:30])=[CH:32][CH:33]=1)([O-:24])=[O:23]

参加物

6

反応物 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 58467984(6S,9S)-6-(2,3-difluorophenyl)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridine-6,9-diol

生成物 1

HCID 58468003(6S,9R)-6-(2,3-difluorophenyl)-6-hydroxy-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-9-yl 4-nitrobenzoate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

In a 250 mL round-bottom flask was dissolved (6S,9S)-6-(2,3-difluorophenyl)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridine-6,9-diol (458 mg, 1.572 mmol) (azeotroped with dry benzene) in tetrahydrofuran (8 mL) to give a light orange solution. 4-Nitrobenzoic acid (394 mg, 2.358 mmol) and triphenylphosphine (619 mg, 2.358 mmol) were added under nitrogen. Diisopropyl azodicarboxylate (0.464 mL, 2.358 mmol) was added dropwise. The mixture was allowed to stir overnight. After 15 h, LCMS showed complete conversion, but the desired product was a minor component. It was concentrated to a light yellow oil and directly purified by FCC (5% ethyl acetate/hexanes to 100%) to afford the desired product (125 mg, 18%) as a white solid. MS(ESI)[M+H+]=441.20.

後処理

  1. customto give a light orange solution
  2. waitAfter 15 h

出典と根拠

ORDレコード
ord-bf4f56cefd6c4951b37598efdd3f57b7
出典データセット
uspto-grants-2012_11
特許番号
US08314117B2

反応ノート

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