期刊
CHEM CATALYSIS
卷 2, 期 5, 页码 1128-1142出版社
CELL PRESS
DOI: 10.1016/j.checat.2022.03.006
关键词
-
资金
- Pharma Innovation Program Singapore (A*STAR) [SERC A19B3a0014]
A photocatalytic method using polysulfide anions as catalysts enables the synthesis of alpha-tertiary amines through alpha-C-H functionalization of a-secondary benzylamines with cyanoarenes or aryl ketones. The key factors include the highly negative oxidation potential of polysulfide dianions and the catenated structure of polysulfide anion radicals, facilitating the construction of sterically congested alpha-tertiary amine scaffolds.
alpha, alpha, alpha- Trisubstituted amines (a-tertiary amines) are an important class of compounds in drug discovery programs. Herein, we report a photocatalytic method to synthesize alpha-tertiary amines using polysulfide anions as photocatalysts that facilitate single-electron transfer (SET) and hydrogen atomtransfer ( HAT) in relays to enable alpha-C-H functionalization of a-secondary benzylamines with cyanoarenes or aryl ketones under irradiation with visible light. The keys enabling advance in the present protocol take advantage of highly negative photoexcited oxidation potential of polysulfide dianions (S-n(2-), n = 4 or 6) to cover a range of cyanoarenes and aryl ketones for their SET reduction as well as the catenated structure of polysulfide anion radicals (S-n(.-), n = 4 or 6) capable of polarity-driven HAT at the hindered a-amino benzylic C-H bond. Thus, ensuing coupling of cyanoarene radical anions or ketyl anion radicals with a-amino benzylic radicals allows for facile construction of sterically congested a-tertiary amine scaffolds.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据