Sodium Dithionite-Mediated Decarboxylative Sulfonylation: Facile Access to Tertiary Sulfones
Sodium Dithionite-Mediated Decarboxylative Sulfonylation: Facile Access to Tertiary Sulfones
复制标题
连二亚硫酸钠介导的脱羧磺酰化：轻松获得叔砜
DOI：
10.1002/anie.202001589
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发表时间：
2020-03-25
影响因子：
16.6
通讯作者：
Jiang, Xuefeng
中科院分区：
文献类型：
--
作者：
Li, Yaping;Chen, Shihao;Jiang, Xuefeng
建立了氧化还原活性酯（n -羟基邻苯二胺酯）、二亚硝酸钠和亲电试剂的直接多组分脱羧交叉偶联，以构建立体体积大的砜。无机盐二亚硝酸钠不仅可以作为二氧化硫源，还可以作为有效的自由基引发剂进行脱羧。值得注意的是，多种天然丰富的羧酸和人工制备的具有多个杂原子和敏感官能团的含羧基药物成功地进行了脱羧磺化，获得了立体体积大的叔砜。机制研究进一步表明脱羧是速率决定步骤，并通过单电子转移（SET）过程在二亚硫酸钠的辅助下发生。
A straightforward multicomponent decarboxylative cross coupling of redox-active esters (N-hydroxyphthalimide ester), sodium dithionite, and electrophiles was established to construct sterically bulky sulfones. The inorganic salt sodium dithionite not only served as the sulfur dioxide source, but also acted as an efficient radical initiator for the decarboxylation. Notably, diverse naturally abundant carboxylic acids and artificially prepared carboxyl-containing drugs with multiple heteroatoms and sensitive functional groups successfully underwent this decarboxylative sulfonylation to provide sterically bulky tertiary sulfones. Mechanistic studies further demonstrated that decarboxylation was the rate-determining step and occurred via a single-electron transfer (SET) process with the assistance of sodium dithionite.