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

反応式

HRID 258160 の反応式
[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]

参加物

7

反応物 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

生成物 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 ester収率 96%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-5088a87e828a4964b04ba3065a3a8cc1
出典データセット
uspto-grants-1993_11
特許番号
US05264586

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