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

반응식

HRID 258160 반응식
[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]

참가 물질

7

반응물 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

생성물 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 ester수율 96%

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 57417360Sodium chloride; water용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-5088a87e828a4964b04ba3065a3a8cc1
출처 데이터셋
uspto-grants-1993_11
특허 번호
US05264586

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