Triethylamine → (S)-ethyl 2-tert-butoxy-2-(6-(cyclopropylethynyl)-1-hydroxy-3-methylnaphthalen-2-yl)acetate

HRID 926189노트

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HRID 926189 반응식
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([O:12][Si](CC)(CC)CC)=[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.[CH:32]1([C:35]#[C:36][Si](C)(C)C)[CH2:34][CH2:33]1.C(N(CC)CC)C.[F-].[Cs+]>C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[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:36]#[C:35][CH:32]3[CH2:34][CH2:33]3)[CH:3]=2)[C:8]=1[OH:12])[C:21]([O:23][CH2:24][CH3:25])=[O:22])([CH3:28])([CH3:30])[CH3:29]

참가 물질

8

반응물 4

HCID 8471TriethylamineHCID 25953Cesium fluorideHCID 2758018(Cyclopropylethynyl)trimethylsilaneHCID 89681729(S)-ethyl 2-(6-bromo-3-methyl-1-(triethylsilyloxy)naphthalen-2-yl)-2-tert-butoxyacetate

생성물 1

HCID 89681789(S)-ethyl 2-tert-butoxy-2-(6-(cyclopropylethynyl)-1-hydroxy-3-methylnaphthalen-2-yl)acetate

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418397HCID 178418397, 화합물촉매HCID 8857Ethyl Acetate용매

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온도
110 °C

실험 절차

A Smith process vial was charged (S)-ethyl 2-(6-bromo-3-methyl-1-(triethylsilyloxy)naphthalen-2-yl)-2-tert-butoxyacetate (151 mg, 0.287 mmol), (cyclopropylethynyl)trimethylsilane (195 mg, 0.316 mmol), Pd(PPh3)4 (33 mg, 0.03 mmol), CuI (55 mg, 0.28 mmol), triethylamine (0.12 mL, 0.86 mmol), cesium fluoride (144 mg, 0.95 mmol) and flushed with nitrogen. THF (3 mL) was added and mixture sparged with nitrogen for 10 minutes and then heated in microwave at 110° C. for 1 hour. 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 100% ethyl acetate/hexanes) to give (S)-ethyl 2-tert-butoxy-2-(6-(cyclopropylethynyl)-1-hydroxy-3-methylnaphthalen-2-yl)acetate. LCMS-ESI− (m/z): [M−H]− calcd for C24H27O4: 379.48. Found: 379.20.

후처리

  1. customflushed with nitrogen
  2. additionTHF (3 mL) was added
  3. custommixture sparged with nitrogen for 10 minutes
  4. customReaction mixture
  5. washwashed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by flash column chromatography (silica gel, 0 to 100% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-18cf909a29854e51bf1a0e6629e0d43f
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09284323B2

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