Synthesis of novel 2-deoxy-β-benzyl-C-glycosides by highly stereo- and chemoselective hydrogenation of exo-glycals

•Synthesis of exo-glycals by the Wittig reaction of glycosyl phosphonium salts.•Effective and selective hydrogenation using Pd/C(en)catalyst.•Optimization of experimental conditions.•Synthesis of novel 2-deoxy-β-benzyl-C-glycosides. Novel 2-deoxy-β-benzyl-C-glycosides were prepared in good yields and excellent stereoselectivity by a route involving the Wittig reaction of glycosyl phosphonium salts and reduction of exo-glycals as key steps. Hydrogenation of benzyl protected enol ethers was performed with Pd/C(en) as an effective chemoselective catalyst to afford exclusively β anomers.