반응 #47141

반응 방정식

triflic anhydride

ketone

1,1′-[[(Propane-1,3-diyl)dioxy]bis[(11S,11aS)-10-(2,2,2-trichloroethoxycarbonyl)-11-(tert-butyldimethylsilyloxy)-7-methoxy-2-oxo-1,2,3,10,11,11a-hexahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one]]

pyridine

→

triflate

수율 61.0%

1,1′-[[(Propane-1,3-diyl)dioxy]bis[(11S,11aS)-10-(2,2,2-trichloroethoxycarbonyl)-11-(tert-butyldimethylsilyloxy)-7-methoxy-2-[[(trifluoromethyl)sulfonyl]oxy]-1,10,11,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one]]

수율 61.0%

용매

EtOAc hexane

반응 조건

후처리

1. 1
   기타the complete consumption of the starting material
2. 2
   workup.ADDITIONThe mixture was poured into cold saturated NaHCO3 (60 mL)
3. 3
   추출extracted with DCM (3×80 mL)
4. 4
   세척The combined organic layers were then washed with saturated CuSO4 (2×125 mL), brine (125 mL)
5. 5
   건조dried (MgSO4)
6. 6
   여과Filtration and evaporation of the solvent
7. 7
   기타afforded the crude product which
8. 8
   기타was purified by flash column chromatography (80:20 v/v hexane/EtOAc)

실험 절차

Anhydrous triflic anhydride (3.09 mL, 5.19 g, 18.4 mmol, 22 eq) taken from a freshly opened ampule was added rapidly in one portion to a vigorously stirred solution of ketone 12 (0.98 g, 0.84 mmol) and anhydrous pyridine (1.49 mL, 1.46 g, 18.4 mmol, 22 eq) in dry DAM (50 mL) at room temperature under a nitrogen atmosphere. The initial precipitate dissolved gradually and the solution eventually turned a dark red colour. The reaction mixture was allowed to stir for 4.5 h when TLC (80:20 v/v EtOAc/hexane) revealed the complete consumption of the starting material. The mixture was poured into cold saturated NaHCO3 (60 mL) and extracted with DCM (3×80 mL). The combined organic layers were then washed with saturated CuSO4 (2×125 mL), brine (125 mL) and dried (MgSO4). Filtration and evaporation of the solvent afforded the crude product which was purified by flash column chromatography (80:20 v/v hexane/EtOAc) to afford triflate 13 as a light yellow glass (0.74 mg, 61%): [α]25 D=+46.0° (c=0.33, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.23 (s, 2H, H6), 7.19 (s, 2H, H3), 6.77 (s, 2H, H9), 5.94 (d, 2H, J=8.9 Hz, H11), 5.23 (d, 2H, J=12.0 Hz, Troc CH2), 4.31-4.28 (m, 2H, OCH2CH2CH2O), 4.18 (d, 2H, J=12.2 Hz, Troc CH2), 4.15-4.13 (m, 2H, OCH2CH2CH2O), 3.95-3.91 (m, 8H, OCH3×2, H11a), 3.35 (dd, 2H, J=11.0, 16.6 Hz, H1), 2.84 (d, 2H, J=16.6 Hz, H1), 2.46-2.44 (m, 2H, OCH2CH2CH2O), 0.89 (s, 18H, TBS CH3×6), 0.29 and 0.26 (s×2, 12H, TBS CH3×4); 13C NMR (100.6 MHz, CDCl3) δ 164.9 (Cquat), 153.6 (Cquat), 151.0 (Cquat), 149.5 (Cquat), 136.0 (Cquat), 127.7 (Cquat), 123.9 (Cquat), 121.0 (C3), 114.0 (C9), 110.9 (C6), 95.1 (Troc CCl3), 86.3 (C11), 74.8 (Troc CH2), 65.0 (OCH2CH2CH2O), 60.6 (C11a), 56.2 (OCH3), 34.4 (C1), 28.8 (OCH2CH2CH2O), 25.6 (TBS CH3), 17.8 (TBS Cquat); IR (CHCl3) 3020, 2957, 2860, 1725, 1674, 1651, 1604, 1516, 1466, 1454, 1431, 1409, 1329, 1312, 1274, 1216, 1138, 1113, 1083, 1042, 1006, 900, 840, 757, 668, 646, 610 cm−1; MS (ES), m/z (relative intensity) 1461 ([M+21]+., 100), 1440 (M+., 55).

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