Diisobutylaluminum hydride → 3-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole

関与物質

反応条件

反応手順

The crude ester 11 (0.85 g, 2.28 mmol) from the preceding procedure was dissolved in THF (25 mL) and added dropwise over 20 min to a stirred solution of DIBAL (9.1 mL of a 1M solution in toluene, 9.1 mmol) in THF (30 mL) under N2 at 0° C. The mixture was stirred for a further 30 min at 0° C., then poured into ice-cold 2 N HCl (40 mL) and extracted twice with EtOAc. The combined extracts were dried (Na2SO4) and concentrated under reduced pressure below 30° C. and the residue was chromatographed on silica gel. Elution with CH2Cl2EtOAc (4:1) afforded a crude product which was crystallised from CH2Cl2 /iPr2O/petroleum ether to give 3-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole (12) (0.48 g, 61%). A sample recrystallised from iPr2O/petroleum ether had mp 176° C. 1H NMR (CDCl3) δ(br s, 1 H, H-9), 8.42 (br s, 1 H, H-7), 7.88 (d, J=7.9 Hz, 1 H, H-4), 7.62-7.51 (m, 2 H, H5,6), 4.30 (m, 1 H, H-2), 4.17 (dd, J=11.4, 9.5 Hz, 1 H, H-2), 4.04-3.93 (m, 2 H, H-3, CHHOH), 383-3.74 (m, 1 H, CHHOH), 1.61 (s, 9 H, C(CH3)3).

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