Synthesis of Ketodeoxysugars from Acylated Pyranosides Using Photoredox Catalysis and Hydrogen Atom Transfer
Synthesis of Ketodeoxysugars from Acylated Pyranosides Using Photoredox Catalysis and Hydrogen Atom Transfer
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DOI：
10.1021/acscatal.1c03050
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发表时间：
2021-08-23
期刊：
影响因子：
12.9
通讯作者：
Taylor, Mark S.
中科院分区：
文献类型：
--
作者：
Turner, Julia A.;Rosano, Nicholas;Taylor, Mark S.
光氧化还原催化剂、氢原子转移介体和氢键受体助催化剂的组合作用已被用于实现吡喃糖苷衍生的酯转化为酮脱氧糖。酰基的位置决定了脱氧位点，使得能够制备2-脱氧-和4-脱氧酮糖衍生物。这些产物是生物活性次级代谢产物中稀有糖组分的有用前体。计算研究是一致的自由基lyaselike机制，其中的关键消除步骤进行通过1，2-酰氧基迁移的自由基中间体。
The combined action of a photoredox catalyst, a hydrogen atom transfer mediator, and a hydrogen bond acceptor cocatalyst has been used to achieve the transformation of pyranoside-derived esters into ketodeoxysugars. The position of the acyl group dictates the site of deoxygenation, enabling the preparation of 2-deoxy- and 4-deoxyketosugar derivatives. The products are useful precursors to rare sugar components of bioactive secondary metabolites. Computational studies are consistent with a radical lyaselike mechanism wherein the key elimination step proceeds via 1,2-acyloxy migration in the radical intermediate.