1,2-Dichlorobenzene → (1R,2S,3S,4R,5S)-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-1-(hydroxymethyl)-7-methyl-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol

Participants

Reaction Steps

To a solution of [(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-7-methyl-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 8c (258 mg, 0.37 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 15 mL) were added o-dichlorobenzene (0.21 mL, 1.82 mmol) and 10% Pd/C (19.3 mg, 0.18 mmol) in turn. The mixture was stirred at room temperature under H2 for 4.5 hours and filtered. The filter cake was washed with a methanol/tetrahydrofuran mixture (v/v=4/1, 10 mL×2). The combined filtrates were concentrated in vacuo. The residue was purified by prep-HPLC to give the title compound 8 as white powder (98 mg, 59%, HPLC: 97.2%). The compound was characterized by the following spectroscopic data: MS (ESI, pos. ion) m/z: 451.1[M+H]+; and 1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.43-7.36 (m, 2H), 7.30 (d, 1H), 7.09 (d, 2H), 6.82 (d, 2H), 5.15 (d, 1H), 4.99 (d, 1H), 4.92 (d, 1H), 4.74 (t, 1H), 3.96 (m, 5H), 3.76 (dd, 1H), 3.62 (m, 2H), 3.51 (dd, 1H), 3.40 (d, 1H), 1.36 (d, 3H), 1.29 (t, 3H).

Provenance & Evidence