반응 #47143

반응 방정식

17

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

→

glass

수율 38.0%

1,1′-[[(Propane-1,3-diyl)dioxy]bis[(11aS)-7-methoxy-2-ethynylphenyl-1,11a-dihydro-5H-pyrrolo[2,1-c][1,4]benzodiazepine-5-one]]

수율 38.0%

용매

THF

반응 조건

후처리

1. 1
   workup.STIRRINGto stir for 45 min when TLC
2. 2
   기타the complete consumption of the starting material
3. 3
   여과The solids were filtered
4. 4
   세척rinsed with H2O and CHCl3
5. 5
   추출The aqueous layer was extracted with CHCl3 (3×25 mL)
6. 6
   세척washed with H2O (50 mL), brine (50 mL)
7. 7
   건조dried (MgSO4)
8. 8
   여과Filtration and evaporation of solvent
9. 9
   기타afforded the crude product which
10. 10
    기타was purified by flash column chromatography (99.8:0.2 v/v CHCl3/MeOH

실험 절차

10% Cd/Pd couple (314 mg, 2.55 mmol, 20 eq) was added to a rapidly stirring mixture of 17 (162 mg, 0.13 mmol), THF (4 mL) and 1 N NH4OAc (4 mL). The reaction mixture was allowed to stir for 45 min when TLC showed the complete consumption of the starting material. The solids were filtered and rinsed with H2O and CHCl3. The aqueous layer was extracted with CHCl3 (3×25 mL) and the organic extracts were combined, washed with H2O (50 mL), brine (50 mL) and dried (MgSO4). Filtration and evaporation of solvent afforded the crude product which was purified by flash column chromatography (99.8:0.2 v/v CHCl3/MeOH then gradient to 97.5:2.5 v/v CHCl3/MeOH) to afford ZC-209 as a yellow glass (33 mg, 38%): 1H NMR (400 MHz, CDCl3) δ 7.79 (d, 2H, J=3.9 Hz, H11), 7.42 (s, 2H, H6), 7.39-7.37 (m, 4H, H15), 7.26-7.19 (m, 8H, H3, H16 and H17), 6.78 (s, 2H, H9), 4.30-4.19 (m, 6H, OCH2CH2CH2O and H11a), 3.86 (s, 6H, OCH3×2), 3.36 (dd, 2H, J=11.7, 16.4 Hz, H1), 3.18 (dd, 2H, J=5.4, 16.4 Hz, H1), 2.37-2.34 (m, 2H, OCH2CH2CH2O); 13C NMR (100.6 MHz, CDCl3) δ 162.0 (C11), 161.3 (Cquat), 151.4 (Cquat), 148.2 (Cquat), 140.3 (Cquat), 132.8 (C3), 131.4 (C15), 128.4 (C16 and C17), 122.9 (Cquat), 118.7 (Cquat), 112.0 (C6), 111.2 (C9), 105.1 (Cquat), 94.3 (Calkyne), 83.3 (Calkyne), 65.5 (OCH2CH2CH2O), 56.2 (OCH3), 53.8 (C11a), 37.9 (C1), 28.8 (OCH2CH2CH2O); MS (ES), m/z (relative intensity) 729 (M+., 100).

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