Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
Org Biomol Chem. 2018 Mar 28;16(13):2269-2276. doi: 10.1039/c7ob02966g.
It was established that 2-O-benzoyl-3,4,6-tri-O-benzyl protected β-SEt, β-SPh and β-SBox glucosyl donors are not superarmed when using the NIS/TfOH promoter system, but instead have a similar reactivity as their classically armed tetra-O-benzyl protected glucosyl counterparts. The β-SBox 2-O-benzoyl-3,4,6-tri-O-benzyl glucosyl donor, however, was found to be superarmed under DMTST activation. Our studies have shown that the increased reactivity of the β-SBox 2-O-benzoyl-3,4,6-tri-O-benzyl glucosyl donor with DMTST activation could be a unique case, and that the high reactivity of glucosyl donors with the 2-O-benzoyl-3,4,6-tri-O-benzyl protection pattern is not general as earlier suggested.
研究结果表明，在使用 NIS/TfOH 引发体系时，2-O-苯甲酰基-3,4,6-三-O-苄基保护的β-SEt、β-SPh 和 β-SBox 葡萄糖基供体并非超强亲核试剂，其反应活性与传统的四-O-苄基保护的葡萄糖基供体类似。然而，我们发现 DMTST 活化的β-SBox 2-O-苯甲酰基-3,4,6-三-O-苄基葡萄糖基供体具有超强亲核试剂的性质。我们的研究表明，DMTST 活化下β-SBox 2-O-苯甲酰基-3,4,6-三-O-苄基葡萄糖基供体反应活性的增加可能是一个特殊情况，而之前所提出的 2-O-苯甲酰基-3,4,6-三-O-苄基保护模式的葡萄糖基供体具有高反应活性并非普遍现象。
