1,8-Diazabicyclo(5.4.0)undec-7-ene → (S)-5-azido-5,6,7,8-tetrahydronaphthalene-1-carbonitrile

HRID 1053736ノート

反応式

HRID 1053736 の反応式
O[C@@H:2]1[CH2:11][CH2:10][CH2:9][C:8]2[C:7]([C:12]#[N:13])=[CH:6][CH:5]=[CH:4][C:3]1=2.C1C=CC(P([N:28]=[N+:29]=[N-:30])(C2C=CC=CC=2)=O)=CC=1.C1CCN2C(=NCCC2)CC1>C1(C)C=CC=CC=1>[N:28]([C@H:2]1[CH2:11][CH2:10][CH2:9][C:8]2[C:7]([C:12]#[N:13])=[CH:6][CH:5]=[CH:4][C:3]1=2)=[N+:29]=[N-:30]

参加物

5

反応物 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 58355020(R)-5-hydroxy-5,6,7,8-tetrahydronaphthalene-1-carbonitrile

生成物 1

HCID 58354960(S)-5-azido-5,6,7,8-tetrahydronaphthalene-1-carbonitrile収率 72.6%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
0 °C

実験手順

A stirring solution of (R)-5-hydroxy-5,6,7,8-tetrahydronaphthalene-1-carbonitrile INT-2 (3.00 g, 17.32 mmol) in toluene (16 mL) under N2, was cooled to 0° C. DPPA (9.53 g, 34.64 mmol) was added, followed by dropwise addition of DBU (3.16 mL, 20.78 mmol) over 20 min. The mixture was stirred at 0° C. for 4 h then slowly warmed to room temperature over 2 h and then concentrated. The resulting crude mixture was diluted with EA and washed with NaHCO3. The combined organic layers were washed with brine, dried over Na2SO4, and chromatographed (EA/hexane) to provide 2.49 g (72.6%) of (S)-5-azido-5,6,7,8-tetrahydronaphthalene-1-carbonitrile INT-6 as a white solid. LCMS-ESI (m/z) calculated for C11H10N4: 198.2; found 156.1 [M−N3]+, tR=3.65 min. 1H NMR (400 MHz, CDCl3) δ 7.60 (dd, J=7.6, 1.2 Hz, 1H), 7.56 (dd, J=7.8, 0.6 Hz, 1H), 7.33 (t, J=7.7 Hz, 1H), 4.59 (t, J=4.4 Hz, 1H), 3.08 (dt, J=18.0, 5.1 Hz, 1H), 2.99-2.83 (m, 1H), 2.15-1.96 (m, 3H), 2.00-1.81 (m, 1H). 13C NMR (101 MHz, DMSO) δ 141.05, 135.58, 133.47, 132.66, 126.58, 117.43, 113.21, 58.74, 28.28, 27.54, 18.27.

後処理

  1. temperaturethen slowly warmed to room temperature over 2 h
  2. concentrationconcentrated
  3. additionThe resulting crude mixture was diluted with EA
  4. washwashed with NaHCO3
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. customchromatographed (EA/hexane)

出典と根拠

ORDレコード
ord-f4a55d608be84608aad2fe4f18178583
出典データセット
uspto-grants-2016_07
特許番号
US09394264B2

反応ノート

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