Butylamine → (E)-2-[(5R)-4,5,6,7-Tetrahydro-5-[(triethylsilyl)oxy]-5-[(3Z)-6-trimethylsilyl-3-hexen-1,5-diynyl]spiro[2,1-benzisoxazole-7,2'-[1,3]dioxolan]-4-ylidene]acetic acid, methyl ester

HRID 258161Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 258161
Cl/[CH:2]=[CH:3]\[C:4]#[C:5][Si:6]([CH3:9])([CH3:8])[CH3:7].C(N)CCC.[C:15]([C@:17]1([O:35][Si:36]([CH2:41][CH3:42])([CH2:39][CH3:40])[CH2:37][CH3:38])[CH2:18][C:19]2([C:24]3[C:25](/[C:29]/1=[CH:30]\[C:31]([O:33][CH3:34])=[O:32])=[CH:26][O:27][N:28]=3)[O:23][CH2:22][CH2:21][O:20]2)#[CH:16]>C1C=CC=CC=1.[Cl-].[Na+].O.[Cu]I>[CH2:41]([Si:36]([CH2:37][CH3:38])([CH2:39][CH3:40])[O:35][C@@:17]1([C:15]#[C:16]/[CH:2]=[CH:3]\[C:4]#[C:5][Si:6]([CH3:9])([CH3:8])[CH3:7])[CH2:18][C:19]2([C:24]3[C:25](/[C:29]/1=[CH:30]\[C:31]([O:33][CH3:34])=[O:32])=[CH:26][O:27][N:28]=3)[O:23][CH2:22][CH2:21][O:20]2)[CH3:42]

Komponenten

7

Edukt 3

HCID 8007ButylamineHCID 10920792(Z)-(4-chloro-3-buten-1-ynyl)trimethylsilaneHCID 15736872(E)-2-[(5R)-5-Ethynyl-4,5,6,7-tetrahydro-5-[(triethylsilyl)oxy] spiro[2,1-benzisoxazole-7,2'-[1,3]dioxolan]-4-ylidene]acetic acid, methyl ester

Produkt 1

HCID 15736873(E)-2-[(5R)-4,5,6,7-Tetrahydro-5-[(triethylsilyl)oxy]-5-[(3Z)-6-trimethylsilyl-3-hexen-1,5-diynyl]spiro[2,1-benzisoxazole-7,2'-[1,3]dioxolan]-4-ylidene]acetic acid, methyl esterAusbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 241BenzeneLösungsmittel2×HCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

(Z)-(4-chloro-3-buten-1-ynyl)trimethylsilane (1.41 mL, 8.16 mmol) and n-butylamine (0.81 mL, 8.16 mmol) were added to a solution of Pd(Ph3)4 (628 mg, 0.54 mmol) in benzene (25 mL). The solution was stirred at 25° C. for 15 minutes and then added to a mixture of Compound 61 (2.204 g, 5.44 mmol) and CuI (207 mg, 1.09 mmol) in benzene (25 mL) at zero degrees C. The solution was stirred two hours at zero degrees C, poured into brine (100 mL) and extracted with dichloromethane (3×100 mL). The organic extracts were dried (Na2SO4), concentrated and purified by flash chromatography (10 percent Et2O in petroleum ether) to give Compound 62 (2.606 g, 91 percent) as a colorless oil; Rf =0.46 (30% Et20 in petroleum ether); [a]D25 =+17.4° (c .2.7 , CH2Cl2); IR (thin film) νmax 1720 cm-1 ; 1H NMR (500 MHz, CDCl3) δ 9.50 (s, 1 H, C=CH--O), 6.65 (s, 1 H, C=CH--CO2), 5.86 (ABq, J =11.0 Hz, Dn =30 Hz, 2 H, CH=CH), 4.38-4.29 (m, 2 H, ethylene ketal), 4.15-4.09 (m, 2 H, ethylene ketal), 3.74 (s, 3 H, CO2Me), 2.67 (ABq, J =14.1 Hz, Dn =61 Hz, 2 H, CH2), 0.89 (t, J =7.3 Hz, 9 H, Si(CH2CH3)3), 0.66 (m, 6 H, Si(CH2CH3)3), 0.17 (s, 9 H, SiMe3); 13C NMR (125 MHz, CDCl3) δ 166.6, 161.2, 161.0, 143.7, 121.2, 118.6, 114.9, 112.0, 103.5, 101.3, 100.7, 95.5, 85.7, 72.1, 65.0, 64.6, 51.5, 50.0, 6.8, 5.9, -0.4; FAB HRMS (NBA/CsI) m/e 660.1213, M+Cs+ calcd for C27H37NO6Si2 660.1214.

Aufarbeitung

  1. stirringThe solution was stirred two hours at zero degrees C
  2. extractionextracted with dichloromethane (3×100 mL)
  3. dry with materialThe organic extracts were dried (Na2SO4)
  4. concentrationconcentrated
  5. custompurified by flash chromatography (10 percent Et2O in petroleum ether)

Quellen und Nachweise

ORD-Eintrag
ord-2714939bb0f24a4489578f02be6655fa
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05264586

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