Methanol → (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

HRID 258160

Reaktionsgleichung

Reaktionsgleichung von HRID 258160
[C:1]([C@:3]1([OH:21])[CH2:4][C:5]2([C:10]3[C:11](/[C:15]/1=[CH:16]\[C:17]([O:19][CH3:20])=[O:18])=[CH:12][O:13][N:14]=3)[O:9][CH2:8][CH2:7][O:6]2)#[CH:2].N1C(C)=CC=CC=1C.FC(F)(F)S(O[Si:36]([CH2:41][CH3:42])([CH2:39][CH3:40])[CH2:37][CH3:38])(=O)=O.CO>ClCCl.[Cl-].[Na+].O>[C:1]([C@:3]1([O:21][Si:36]([CH2:41][CH3:42])([CH2:39][CH3:40])[CH2:37][CH3:38])[CH2:4][C:5]2([C:10]3[C:11](/[C:15]/1=[CH:16]\[C:17]([O:19][CH3:20])=[O:18])=[CH:12][O:13][N:14]=3)[O:6][CH2:7][CH2:8][O:9]2)#[CH:2]

Komponenten

7

Edukt 4

HCID 887MethanolHCID 79372,6-LutidineHCID 2733308Triethylsilyl trifluoromethanesulphonateHCID 15736871(E)-2-[(5R)-5-Ethynyl-4,5,6,7-tetrahydro-5-hydroxyspiro[2,1-benzisoxazole-7,2'-[1,3]dioxolan]-4-ylidene]acetic acid, methyl ester

Produkt 1

HCID 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 esterAusbeute 96 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

A solution of Compound 60 (1.657 g, 5.69 mmol) in dichloromethane (10 mL) was treated with 2,6-lutidine (2.00 mL, 17.1 mmol) and triethylsilyl trifluoromethanesulfonate (2.58 mL, 11.4 mmol) at zero degrees C. The solution was stirred 30 minutes, anhydrous methanol (2 mL) was added, the mixture was poured into brine (50 mL) and extracted with dichloromethane (3×50 mL). The organic extracts were dried (Na2SO4), concentrated and purified by flash chromatography (20% Et2O in petroleum ether) to give Compound 61 (2.204 g, 96 percent) as a white solid, m.p. =108 °-109° C. (from CH2Cl2); Rf =0.43 (30 percent Et2O in petroleum ether); [a]D25 =-15.4° (c 2.8, CH2Cl2); IR (thin film) νmax 3307, 2116, 1721, 1646 cm-1 ; 1H NMR (500 MHz, CDCl3) δ 9.50 (s, 1 H, C=CH--O), 6.57 (s, 1 H, C=CH--CO2), 4.38-4.31 (m, 2 H, ethylene ketal), 4.18-4.10 (m, 2 H, ethylene ketal), 3.74 (s, 3 H, CO2Me), 2.66 (s, 1 H, C}C--H), 2.61 (ABq, J =14.0 Hz, Δν =34 Hz, 2 H, CH2), 0.92 (t, J =7.9 Hz, 9 H, Si(CH2CH3)3), 0.70 (q, J =7.9 Hz, 6 H, Si(CH2CH3)3); 13C NMR (125 MHz, CDCl3) δ 166.5, 161.3, 160.7, 143.8, 114.5, 111.9, 100.6, 83.2, 76.9, 70.9, 65.0, 64.8, 51.6, 49.8, 6.8, 5.9; FAB HRMS (NBA/CsI) m/e 538.0652, M+Cs+ calcd for C20H27NO6Si 538.0662.

Aufarbeitung

  1. extractionextracted with dichloromethane (3×50 mL)
  2. dry with materialThe organic extracts were dried (Na2SO4)
  3. concentrationconcentrated
  4. custompurified by flash chromatography (20% Et2O in petroleum ether)

Quellen und Nachweise

ORD-Eintrag
ord-5088a87e828a4964b04ba3065a3a8cc1
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05264586

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