Triethylamine → (S)-ethyl 2-tert-butoxy-2-(3-methyl-6-(prop-1-ynyl)-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 926186ノート

反応式

HRID 926186 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([O:12][S:13]([C:16]([F:19])([F:18])[F:17])(=[O:15])=[O:14])=[C:7]([C@H:20]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:6]([CH3:31])=[CH:5]2.[C:32]([Sn](CCCC)(CCCC)CCCC)#[C:33][CH3:34].C([O-])(O)=O.[Na+].C(N(CC)CC)C>[Pd+2]>[C:27]([O:26][C@@H:20]([C:7]1[C:6]([CH3:31])=[CH:5][C:4]2[C:9](=[CH:10][CH:11]=[C:2]([C:32]#[C:33][CH3:34])[CH:3]=2)[C:8]=1[O:12][S:13]([C:16]([F:19])([F:17])[F:18])(=[O:15])=[O:14])[C:21]([O:23][CH2:24][CH3:25])=[O:22])([CH3:28])([CH3:29])[CH3:30]

参加物

6

反応物 4

HCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 2733165Tributyl(prop-1-yn-1-yl)stannaneHCID 89681724(S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-tert-butoxyacetate

生成物 1

HCID 118027238(S)-ethyl 2-tert-butoxy-2-(3-methyl-6-(prop-1-ynyl)-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

試薬・触媒・溶媒 1

HCID 105144Allyl(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)chloropalladium(II)触媒

反応条件

温度
120 °C

実験手順

A Smith process vial was charged (S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-tert-butoxyacetate (55 mg, 0.104 mmol), (1-Propynyl)tributylstannane (35 μL, 0.115 mmol), Chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2-aminoethyl)phenyl)]palladium(II) (8 mg, 0.01 mmol), NaHCO3 (4 mg, 0.05 mmol), triethylamine (44 μL, 0.3 mmol) and flushed with nitrogen. DMF (2.0 mL) was added and mixture sparged with nitrogen for 10 minutes and then heated in microwave at 120° C. for 1 hour. The reaction mixture was diluted with ethyl acetate and washed with brine, dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes) to give (S)-ethyl 2-tert-butoxy-2-(3-methyl-6-(prop-1-ynyl)-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate. 1H NMR (400 MHz, CDCl3): δ 7.94 (d, J=4.4 Hz, 1H), 7.80 (s, 1H), 7.56 (s, 1H), 7.50 (d, J=4.6 Hz, 1H), 5.63 (s, 1H), 4.08 (m, 2H), 2.52 (s, 3H), 2.08 (s, 3H), 1.21 (s, 9H), 1.18 (t, 3H).

後処理

  1. customflushed with nitrogen
  2. additionDMF (2.0 mL) was added
  3. custommixture sparged with nitrogen for 10 minutes
  4. additionThe reaction mixture was diluted with ethyl acetate
  5. washwashed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-92e1eae0849b4b8ab5a481b107102bb4
出典データセット
uspto-grants-2016_03
特許番号
US09284323B2

反応ノート

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