Synthesis of three deoxy-sophorose derivatives for evaluating the requirement of hydroxy groups at position 3 and/or 3' of sophorose by 1,2-β-oligoglucan phosphorylases

Abstract

Sophorose (Sop₂) is known as a powerful inducer of cellulases in Trichoderma reesei, and in recent years 1,2-β-D-oligoglucan phosphorylase (SOGP) has been found to use Sop₂ in synthetic reactions. From the structure of the complex of SOGP with Sop₂, it was predicted that both the 3-hydroxy group at the reducing end glucose moiety of Sop₂ and the 3'-hydroxy group at the non-reducing end glucose moiety of Sop₂ were important for substrate recognition. In this study, three kinds of 3- and/or 3'-deoxy-Sop₂ derivatives were synthesized to evaluate this mechanism. The deoxygenation of the 3-hydroxy group of D-glucopyranose derivative was performed by radical reduction using a toluoyl group as a leaving group. The utilization of a toluoyl group that plays two roles (a leaving group for the deoxygenation and a protecting group for a hydroxy group) resulted in efficient syntheses of the three target compounds. The NMR spectra of the two final compounds (3-deoxy- and 3,3'-dideoxy-Sop₂) suggested that the glucose moiety of the reducing end of Sop₂ can easily take on a furanose structure (five-membered ring structure) by deoxygenation of the 3-hydroxy group of Sop₂. In addition, the ratio of the five- and six-membered ring structures changed depending on the temperature. The SOGPs exhibited remarkably lower specific activity for 3'-deoxy- and 3,3'-dideoxy-Sop₂, indicating that the 3'-hydroxy group of Sop₂ is important for substrate recognition by SOGPs.

Keywords: 1,2-β-D-oligoglucan phosphorylase; 3- and/or 3′-deoxy-sophorose; Furanose; Toluoyl group.