3,3-Dimethyl-1-butyne → HCID 87621577, Verbindung

HRID 883751

Reaktionsgleichung

Reaktionsgleichung von HRID 883751
B(C1CCCCC1)C1CCCCC1.[CH3:14][C:15]([CH3:19])([CH3:18])[C:16]#[CH:17].[Zn](CC)CC.[F:25][C:26]([F:36])([F:35])[C:27]1[CH:34]=[CH:33][C:30]([CH:31]=[O:32])=[CH:29][CH:28]=1.CC([O:40]C([C@H](O)[C@@H](O)C(OC(C)C)=O)=O)C>CC(O[Ti](OC(C)C)(OC(C)C)OC(C)C)C>[C:15]([CH:16]1[O:40][CH:17]1[CH:31]([C:30]1[CH:33]=[CH:34][C:27]([C:26]([F:35])([F:36])[F:25])=[CH:28][CH:29]=1)[OH:32])([CH3:19])([CH3:18])[CH3:14]

Komponenten

7

Edukt 5

HCID 135123,3-Dimethyl-1-butyneHCID 679964-(Trifluoromethyl)benzaldehydeHCID 6453580Diisopropyl tartrateHCID 15879360CID 15879360HCID 178418750HCID 178418750, Verbindung

Produkt 1

HCID 87621577HCID 87621577, VerbindungAusbeute 85 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 178460666HCID 178460666, VerbindungKatalysator

Versuchsvorschrift

The product was prepared by General procedure T using 50 mg (0.28 mmol) Cy2BH, 35 μL (0.28 mmol) 3,3-dimethyl-1-butyne, 0.39 mL (0.78 mmol, 2.0 M in hexanes) Et2Zn, 2.4 mg (0.01 mmol) (−)-MIB, 34 μL (0.25 mmol) p-trifluoromethylbenzaldehyde, 50 μL (0.05 mmol, 1.0 M in hexanes) Ti(OiPr)4, and 10.6 μL (0.05 mmol) (+)-DIPT. The crude product was purified by column chromatography (5% ethyl acetate in hexanes) to afford the title compound in 85% yield (58 mg, 0.21 mmol). threo-diastereomer: Colorless solid. m.p.: 76-79° C.; [α]D20=−10.0 (c=0.27, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 0.90 (s, 10H), 2.89 (d, 1H, J=2.2 Hz), 3.03 (dd, 1H, J=5.5, 2.2 Hz), 4.58 (d, 1H, J=5.4 Hz), 7.53 (d, 2H, J=8.1 Hz), and 7.64 (d, 2H, J=8.1 Hz) ppm; 13C{1H} NMR (CDCl3, 125 MHz): δ 25.7, 30.6, 59.0, 65.3, 73.6, 125.54, 125.58, 125.59, and 126.3 ppm; IR (film): 3411, 3028, 2969, 2927, 2871, 2367, 2332, 1622, 1477, 1460, 1420, 1365, 1331, and 1241 cm−1; HRMS-CI m/z 255.1192 [(M−F)+; calcd for C14H17F2O2: 255.1197]. erythro-diastereomer: Colorless solid. m.p.: 74-75° C.; [α]D20=−32.0 (c=0.10, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 0.83 (s, 9H), 2.30 (br s, 1H), 2.93 (d, 1H, J=2.0 Hz), 3.03 (t, 1H, J=2.6 Hz), 4.90 (d, 1H, J=2.2 Hz), 7.48 (d, 2H, J=8.0 Hz), and 7.60 (d, 2H, J=8.0 Hz) ppm; 13C{1H} NMR (CDCl3, 125 MHz): δ 25.7, 31.6, 57.9, 62.8, 75.6, 125.50, 125.51, 125.53, and 126.6 ppm; IR (film): 3350, 3037, 2955, 2868, 1661, 1620, 1477, 1463, 1414, 1365, and 1327 cm−1; HRMS-CI m/z 255.1192 [(M−F)+; calcd for C14H17F2O2: 255.1197].

Aufarbeitung

  1. customThe product was prepared by General procedure T
  2. customThe crude product was purified by column chromatography (5% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-9b1726c00d824475b6d0080b8a39593d
Quelldatensatz
uspto-grants-2012_08
Patentnummer
US08236976B2

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