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The biologically highly active calichemicin γ 1αI contains the benzoate 1 — glycosylated on the OH group and linked through the ester group (S instead of O), via sugar moieties, to other unusual organic fragments. Compound 1 has now been synthesized in five steps from 3,4,5‐trimethoxytoluene and has proven to be very interesting. It undergoes spontaneous enantiomer resolution upon crystallization and exhibits second harmonic generation activity.

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